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Fuel 165 (2016) 264271

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Fuel
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Removal of sulfonated humic acid from aqueous phase by modified coal


fly ash waste: Equilibrium and kinetic adsorption studies
Chunjiang An a,b, Siqi Yang b, Guohe Huang a,, Shan Zhao a, Peng Zhang a, Yao Yao a
a
b

Institute for Energy, Environment and Sustainable Communities, University of Regina, Regina S4S 0A2, Canada
Institute for Energy, Environment and Sustainability Research, UR-NCEPU, North China Electric Power University, Beijing 102206, China

h i g h l i g h t s

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

 Sulfonated humic acid (SHA) is the

Sulfonated Humic Acid (SHA)


100
Shand-treated A

100

Shand-treated B

95
Removal efficiency (%)

Removal efficiency (%)

important pollutant in oilfield


wastewater.
 SHA could be adsorbed onto modified
fly ash with good removal efficiency.
 The equilibrium and kinetic studies
on SHA adsorption by fly ash were
conducted.
 The adsorption process could be
influenced by aqueous ionic strength.
 Sustainable development can be
achieved for oil and power industries.

80

60

40

Shand f ly ash
Shand-treated A

90
85
80
75
70

Shand-treated B

20

65
60

0
0

0.2

0.4
0.6
Fly ash dosage (mg/L)

0.8

0.1
0.2
0.3
Ionic strength (mol/L)

0.4

Modified Fly Ash


a r t i c l e

i n f o

Article history:
Received 15 July 2015
Received in revised form 26 September 2015
Accepted 16 October 2015
Available online 23 October 2015
Keywords:
Sulfonated humic acid
Fly ash
Modification
Adsorption
Energy pollution control
Green technology

a b s t r a c t
Sulfonated humic acid (SHA) is a representative organic pollutant in oilfield wastewater. This study
investigated the performance of modified fly ash in removal of SHA from aqueous solution. Two types
of raw fly ash, including Shand fly ash (class C) and BD fly ash (class F) were used. X-ray diffraction
and surface area analyses were also implemented to characterize the change of fly ash after modification.
The results showed suitable acid- and microwave-assisted modification could enhance adsorption capacity of fly ash. The efficiency for SHA removal by treated Shand fly ash was higher than that by treated BD
fly ash under the same conditions. Among different factors, pH was the most critical factor which could
influence the adsorption performance of treated fly ash. The SHA removal efficiency increased as modified fly ash dosage increased up to 1 and 6 g/L for Shand and BD fly ash, respectively. Langmuir isotherm
could better fit equilibrium data. Kinetic analysis results showed this process could be well described by
pseudo-second-order model. There was higher adsorption capacity at higher temperature when temperature varied between 15 and 35 C. The addition of NaCl also had influence on the adsorption performance of modified fly ash. The results of this study can help reveal the interactions of SHA pollutant
and fly ash characteristics, which have important implications for the application of adsorption technologies in the treatment of oilfield wastewater.
2015 Elsevier Ltd. All rights reserved.

1. Introduction
Corresponding author.
E-mail address: huang@iseis.org (G. Huang).
http://dx.doi.org/10.1016/j.fuel.2015.10.069
0016-2361/ 2015 Elsevier Ltd. All rights reserved.

Oil production is usually accompanied by wastewater generation [1]. The amount of wastewater can be as much as seven to

265

C. An et al. / Fuel 165 (2016) 264271

ten times the amount of oil produced during the lifetime of oilfield
[2]. Oilfield wastewater is a complex mixture containing different
inorganic and organic components [3]. There is a particular concern regarding the organic compounds in oilfield wastewater
because they may cause serious problems to ecosystem once in
the environment. As a representative organic component in oilfield
wastewater, sulfonated humic acid (SHA) has been widely used as
filtrate reducer and viscosity reducer in oil exploitation and production processes. The existence of SHA may help achieve the good
dispersion and low viscosity for oil recovery flows. However, the
discharge of SHA-contained effluent will inevitably lead to a high
level of COD, BOD, sulfurated pollutants and other toxic substances
in environment. The distribution behaviors of oil compounds and
metal ions in contaminated aqueous phase can be also influenced
in the presence of SHA. It is therefore desired to develop suitable
treatment strategy to remove such toxic pollutant from oilfield
effluent.
In order to meet the requirements of environmental protection,
many efforts have been made to obtain the effective and safe
approaches for treatment of oilfield wastewater. It is known that
biodegradation can be used as an important technique for the
removal of organic pollutants from aqueous phase [47]. This
approach has been also applied in the treatment of pollutants in
oilfield wastewater. Tellez et al. [8] evaluated the performance of
a field activated sludge treatment system for removing petroleum
hydrocarbons from produced water generated in Southwestern US
oilfield. Freire et al. [9] reported the removal of phenols, ammonium and COD during the biological treatment of oilfield wastewater using a sequencing batch reactor. Although the biological
treatment is a cost-effective method, the high salinity, low temperature and toxic hydrocarbons associated with raw oilfield effluent
are not desirable factors for microbial activity [10]. Recently, some
physicochemical treatment technologies including flotation, ionic
change, chemical oxidation, membrane filtration and irradiation
have been developed for the treatment of oilfield wastewater
[1113]. Among various physicochemical approaches, adsorption
is an important technique in separation and purification [14]. It
is a surface-based process involving the adhesion of pollutants
from liquid to solid. Adsorption-based technique has been applied
in the treatment of domestic and industrial wastewater. However,
knowledge about the adsorption of complex organic compound
from oilfield wastewater at adsorbentliquid interface is still
limited.
There has been an increasing interest in the utilization of natural materials and industrial wastes, which can be taken as an alternative to traditional adsorbents. Fly ash is generated as the byproduct in coal combustion [15,16]. Its components can vary
widely, depending upon the coal sources and combustion conditions [17,18]. The effectiveness of removing phosphate, fluoride,
boron and heavy metals from effluent using fly ash has been shown
[1922]. The adsorption of dyes, phenols, herbicides, polycyclic
aromatic hydrocarbons, and other organic compounds have been
also reported in previous studies [2328]. Although these findings
are encouraging, a number of issues about the adsorption characteristics of pollutants on fly ash surface are poorly understood.
Few previous studies have been carried out to explore the adsorption of oilfield pollutants on fly ash. Moreover, fly ash can be used
in adsorption after some minor treatments. Pengthamkeerati et al.
[29] investigated the chemical modifications of coal fly ash and
observed the appropriate treatment could improve the sorption
efficiency of phosphate on treated fly ash. Li et al. [30] investigated
the tannin adsorption on coal fly ash treated by HCl. Chowdhury
and Saha [31] evaluated the applicability of alkali-treated fly ash
as adsorbent for the removal of malachite green from aqueous
solution. Cao et al. [32] modified fly ash by polydimethydiallylammonium chloride and explored the adsorption performance of

modified fly ash in dyeing wastewater treatment. Beyond that, little information is available concerning the potential of modified fly
ash in the removal of oilfield organic pollutants from solution.
This study aims to investigate the performance of modified fly
ash in removal of SHA from aqueous solution. Batch experiments
will be conducted to investigate the adsorption characteristics of
SHA onto treated fly ash. The optimum modification conditions
will be determined and the adsorption isotherms and kinetics will
be studied. The effects of adsorbent dosage, contact time, temperature and ionic strength will be also evaluated. The results of this
study can have important implications for the application of
adsorption technologies in the treatment of oilfield wastewater.
As a green technology using waste from one energy sector to treat
the waste from another energy sector, this study can help achieve a
sustainable development for both oil and power industries.
2. Materials and methods
2.1. Chemicals
SHA was used as a representative organic pollutant from oilfield
wastewater. The hydrolysable SHA, a commercial product obtained
from Renqiu Chemical Co., Ltd. (Renqiu, China), was used as adsorbate. It includes 43.94% of organic carbon, 0.45% of total sulfur,
1.69% of hydrogen, and 0.92% of nitrogen. All other chemicals used
were of reagent grade quality or higher.
2.2. Fly ash adsorbent
Two types of fly ash samples were obtained from coal-fired
power plants operated by SaskPower in Saskatchewan, Canada.
They were labeled as Shand fly ash and BD fly ash for the samples
from Shand Power Station and Boundary Dam Power Station,
respectively. The properties of fly ash are shown in Table 1. Prior
to experiments, fly ash was washed in ultrapure water to remove
soluble compounds and dried. Fly ash was treated through
the mixing with HCl solution at a ratio of 1:100 (fly ash weight
(g):liquid volume (mL)). pH of ash-liquid mixture was adjusted
to 3. The modified Shand and BD fly ash were labeled as Shandtreated A and BD-treated A, respectively. Various optimization
approaches have been applied in environmental studies [33,34].
In the process of microwave-assisted modification, the acidmodified fly ash was further treated and a L16 orthogonal array
scheme including four levels was adopted. The sequence of experiments was randomized to avoid any personal or subjective bias.
Shand-treated A and BD-treated A fly ash samples irradiated by
microwave at 400 W for 8 min were labeled as Shand-treated B
and BD-treated B, respectively. All fly ash samples were dried for
24 h at 105 C, screened with 0.25 mm-sieve, and stored in desiccator before use.

Table 1
Properties of the selected fly ash.
Sorbents

Shand fly ash

BD fly ash

Physical form
SiO2 (%)
Al2O3 (%)
Fe2O3 (%)
CaO (%)
SO3 (%)
Loss on ignition (%)
BET surface area (m2/g)
Fineness (retained on No. 325 sieve, %)
Type
Density (g/cm3)

Powder
41.4
19.2
3.47
22.7
3.35
1.38
4.31
17.9
Class C
2.67

Powder
44.7
20.8
4.06
13.9
0.51
0.17
2.28
14.5
Class F
2.36

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C. An et al. / Fuel 165 (2016) 264271

2.3. Adsorption experiments

Table 2
The results of orthogonal design for Shand fly ash modification.

All the adsorption experiments were conducted in 250-mL volumetric flasks with Parafilm sealing. Appropriate amount of fly ash
and 100 mL SHA solution at certain concentration were added to
each conical flask. To investigate the effect of fly ash dosage on
SHA adsorption, different amounts of fly ash ranging from 0.1 to
1 g/L (Shand fly ash) and 16 g/L (BD fly ash) were added into each
conical flask with an initial SHA concentration at 200 mg/L. For the
study of adsorption kinetics, isotherms and effects of ionic
strength, fly ash dosages were 0.55 and 2.8 g/L for the series with
Shand and BD fly ash, respectively. The adsorption isotherms were
obtained at 15, 25 and 35 C with different concentrations of SHA
varying from 0 to 400 g/L. To investigate the effect of ionic
strength, different concentrations of NaCl solution were prepared
by adding appropriate NaCl to SHA solution. The volumetric flasks
containing fly ash and SHA solution were put into the temperaturecontrolled shaker at 200 rpm and 25 C for 6 h to reach adsorption
equilibrium. Then the aqueous samples were taken from flasks and
the concentration of SHA was measured after filtration.
2.4. Analytical methods
The SHA concentration in aqueous solution was determined
through measuring absorbance at maximum wavelength of SHA
(kmax = 400 nm) using a UVVis spectrophotometer (Unico Com.,
China). A YLB-LAB870 pH meter (Schott AG, Germany) was used
to analyze the pH level of solution. The adsorption capacity
(mg/g) and removal efficiency (%) were calculated as follows.

Adsorption capacity C 0  C e V=W

Removal efficiency C 0  C e  100=C 0

where C 0 (mg/L) and C e (mg/L) are the initial and equilibrium SHA
concentrations, respectively. V is the volume of solution in L and W
is the weight of adsorbent in g. The quality assurance/quality control program was followed to ensure the accuracy and reliability
of the collected data. All batch tests were conducted in triplicate
and average values were reported (relative standard deviation less
than 5%). Blank tests were run and corrections were applied if necessary. Experimental runs have been performed by using a SHA containing solution without addition of adsorbent. The corresponding
results confirmed that the initial SHA concentration remained
unchanged during the experiment. It indicated that the reduction
of SHA concentration during adsorption tests was only related to
the presence of the adsorbent. X-ray diffraction (XRD) patterns of
all samples were obtained with a XRD instrument (BRUKER D8
ADVANCE, Germany) using Cu Ka radiation at 40 kV and 40 mA over
the range (2h) of 1080. The specific surface area of fly ash was
determined at 77 K with a TriStar II 3020 (Micromeritics, USA). Statistical calculations and analyses were performed with the use of
the Minitab (Minitab Inc., USA) statistical software package.
3. Results and discussion
3.1. Modification of fly ash
Adsorption efficiency was used to evaluate the performance of
modified fly ash for the removal of SHA from aqueous phase. The
results for adsorption tests using modified fly ash treated under
different conditions are shown in Tables 2 and 3. The maximum
removal efficiency of SHA was obtained when the fly ash was treated under condition #3. Range analysis results showed that the
impact of different factors on the modification decreased in an
order: pH > microwave power > irradiation time. pH was revealed

No.

Level
pH

Microwave power (W)

Reaction time (min)

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
K1
K2
K3
K4
R

3
3
3
3
7
7
7
7
9
9
9
9
11
11
11
11
85.06
72.97
54.14
24.70
60.36

80
240
400
640
80
240
400
640
80
240
400
640
80
240
400
640
55.00
60.56
64.14
57.18
9.14

4
6
8
10
6
4
10
8
8
10
4
6
10
8
6
4
57.68
59.49
61.10
58.61
3.41

Removal
efficiency (%)
78.25
85.94
92.26
83.79
72.14
71.44
75.11
73.2
49.4
55.32
60.58
51.25
20.2
29.52
28.61
20.46

K1, K2, K3, and K4 were the mean values of level 1, 2, 3, and 4 for each factor; R
was the range among the sum sores of level 1, 2, 3, and 4 for each factor.

Table 3
The results of orthogonal design for BD fly ash modification.
No.

1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
K1
K2
K3
K4
R

Level
pH

Microwave power (W)

Reaction time (min)

3
3
3
3
7
7
7
7
9
9
9
9
11
11
11
11
83.35
72.53
51.66
21.19
62.16

80
240
400
640
80
240
400
640
80
240
400
640
80
240
400
640
50.78
58.87
63.18
55.89
12.40

4
6
8
10
6
4
10
8
8
10
4
6
10
8
6
4
55.77
56.10
60.08
56.77
4.30

Removal
efficiency (%)
73.92
83.77
92.83
82.86
66.18
73.48
76.12
74.32
46.99
52.05
58.44
49.14
16.03
26.16
25.31
17.25

K1, K2, K3, and K4 were the mean values of level 1, 2, 3, and 4 for each factor; R
was the range among the sum sores of level 1, 2, 3, and 4 for each factor.

to be the most critical factor which can influence the adsorption


performance of treated fly ash. The optimum pH level for modification is pH 3. Fly ash is formed when molten minerals solidify, while
some closed cavities are generated in the internal structure of a
particle. After the acid treatment, some mineral constituents of
fly ash could be partially dissolved. It can lead to rough surface
and opened cavity which would increase the specific surface area
of fly ash particles. The specific surface area of the modified fly
ash was measured to ascertain whether it could vary with pH.
The surface areas for Shand-treated A and BD-treated A are 5.86
and 2.94 m2/g, respectively, which are all higher than the corresponding values for raw fly ash. It is known that the larger surface
area is usually corresponding with the better adsorption capacity

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C. An et al. / Fuel 165 (2016) 264271

for solid adsorbents. It is expected that the increased surface area


of acid-treated fly ash can provide more available sites for the
adsorption of SHA molecules. A low pH level can facilitate the
enhanced adsorption capacity of fly ash. A similar enhanced
adsorption was observed in which HCl-treated fly ash was used
to remove methylene blue, crystal violet and rhodamine B [35].
Hydrothermal treatment in alkali medium can be also used in
the modification of fly ash. It can lead to the conversion of a significant fraction of fly ash to zeolites [36]. But there will be a stricter
requirement for the modification condition.
In the present study, it was observed that microwave-assisted
treatment can further enhance the adsorption capacity of fly ash.
As the microwave power increased, the value of K gradually
increased and reached the maximum level when the microwave
power was 400 W. A decrease of K was obtained when the microwave power was higher than 400 W. The maximum K was
observed at the reaction time of 8 min. The unburned carbon in
fly ash can also play an important role in the adsorption of pollutants in aqueous phase [37]. Modification by microwave radiation
could result in an increase in the average pore size and hydrophobicity of carbon [38]. Some surface functional groups can change as
a result of the destruction of oxygen-containing functional groups
at high temperatures.
The XRD results show that quartz is the primary crystalline specie in the fly ash samples, while some other components such as
magnetite, hematite and mullite also exist (Fig. 1). This result is

similar with that observed in previous studies [17,39]. The amorphous phase of aluminosilicate could appear in XRD patterns as a
broad halo centered approximately between 22 and 35 (2h)
[40]. After the acid modification, the intensity of magnetite and
hematite for Shand fly ash decreased, indicating the dissolving of
iron-contained components. Peak of mullite in Shand-treated fly
ash increased significantly. As for BD fly ash, hematite and magnetite increased after acid modification and mullite increased after
further microwave treatment. In addition, intensity of quartz was
enhanced in all treated fly ash samples. These results suggest that
the surface of fly ash changed after modification.
3.2. Effect of fly ash dosage on adsorption of SHA
The adsorption of SHA with different fly ash dosages is shown in
Fig. 2. The overall trends of adsorption for different types of fly ash
were similar. When the dosage of fly ash was lower than 0.75 g/L
(Shand) and 4 g/L (BD), the SHA removal efficiency increased significantly as fly ash dosage increased. This trend can be attributed
to the change of fly ash dosage since the initial concentration of
SHA was kept constant. When the fly ash dosage was higher than
0.75 g/L (Shand) and 4 g/L (BD), however, there was no further
increasing in SHA removal efficiency as fly ash dosage varied. The
removal of SHA from aqueous phase is based on the adsorption
of solute on adsorbent, which is mainly a surface phenomenon.
The surface area and surface sites available for adsorption are

(a)

(a)

100

Mu

Q Mu Mu

Ma

Mu
Mu

Ma
Mu Mu

Mu

H Mu
MaMu

Mu H

Mu Ma Ma

H Mu H

Ma
Ma
Mu

Mu

H
H

Removal efficiency (%)

80

60

40

Shand fly ash


Shand-treated A
Shand-treated B

20

0
0

0.2

0.4

0.6

0.8

Fly ash dosage (mg/L)

(b)

(b)

100

Q
Mu
Mu Ma

Mu

Ma
Mu Mu Q
Q Ma
Ma
H
H
Mu

Q
Q

Mu

Mu Ma

Q
H Mu

Ma Mu

Ma

Ma

Mu
Q

Removal efficiency (%)

80

60

40

BD fly ash
BD-treated A
BD-treated B

20
Ma

0
0

Fly ash dosage (mg/L)


Fig. 1. XRD patterns of treated (a) Shand and (b) BD fly ash (Q: Quartz; Ma:
Magnetite; H: Hematite; Mu: Mullite).

Fig. 2. Effect of fly ash dosage on the adsorption of SHA onto (a) Shand fly ash and
(b) BD fly ash.

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C. An et al. / Fuel 165 (2016) 264271

usually proportional to the adsorbent amount. As the fly ash


dosage increased, there would be a corresponding increase in the
adsorption capacity of fly ash. Once the maximum amount of
SHA has been adsorbed, the excess dosage of fly ash would have
no significant influence on the SHA removal efficiency. A faster
adsorption of SHA onto fly ash surface at high fly ash dosage can
be achieved when compared with it at low fly ash dosage. This
result is also similar with that in some previous studies. Kumar
et al. [41] observed removal of methylene blue varied with changing fly ash mass and it increased with increasing adsorbent mass.
Mohan and Gandhimathi [42] reported that the removal efficiency
for heavy metals increased with the increase in fly ash dose from
0.5 to 2 g/L and remained almost constant thereafter. Under the
same condition of fly ash dosage and initial SHA concentration,
there was a lower solute concentration in the solution with treated
fly ash, indicating the corresponding higher removal efficiency
with treated fly ash. At a dosage of 0.75 and 4 g/L, the SHA removal
efficiencies were 98.45% and 98.51% for Shand-treated A and
BD-treated A fly ash, respectively; the SHA removal efficiencies
were 99.85% and 99.78% for Shand-treated B and BD-treated B fly
ash, respectively. The results indicate the treatment of fly ash has
influence on adsorption process. Fly ash surface can be changed
by partial dissolution of mineral components within fly ash and
the radiation of microwave energy. For the treated fly ash, the efficiency for SHA removal by Shand fly ash was significantly higher
(p < 0.05) than that by BD fly ash under the same conditions. This
could be attributed to the different properties between two fly
ash types. The higher loss on ignition of Shand fly ash indicated
that higher carbon residue content was associated with Shand fly
ash when compared with BD fly ash. The residue carbon of fly
ash can play a role in the adsorption performance. The different
carbon contents in two fly ash types can be related to different
adsorption behaviors correspondingly. The higher specific surface
area of the Shand fly ash also provided greater access to adsorption
sites and could help explain its higher capacity for SHA adsorption.
3.3. Adsorption isotherms
To better understand the adsorption process, it is important to
characterize equilibrium adsorption curves [4345]. Langmuir
and Freundlich adsorption isotherm models were used to describe
the data in this study. Isotherm data were fitted to Langmuir
model:

C e =Q e C e =Q m 1=K L Q m

where Q e is the amount of sorbate adsorbed per unit mass of


adsorbent (mg/g), C e is the concentration of sorbate in equilibrium
solution (mg/L), Q m is the adsorption capacity (mg/g), and K L is the
Langmuir adsorption constant (L/mg); and Freundlich model:

Q e K f C 1=n
e

where K f is the Freundlich adsorption coefficient [(mg/kg)/(mg/L)n]


which provides an index of adsorption capacity, and n is the
Freundlich exponent that describes isotherm nonlinearity.

The calculated parameters based on experimental data with the


aid of regression analysis are given in Table 4. The results show
that both of the two isotherm models could well fit the data for
the adsorption of SHA on treated fly ash. The Langmuir model
yields a better (0.8950.998) fit than that of the Freundlich model
(0.7210.960), indicating the formation of monolayer coverage of
SHA molecules at the outer surface of fly ash. The acid- and
microwave-modified fly ash had the similar fitting characteristics.
This result was similar with that in some previous studies. Kumar
et al. [41] analyzed the adsorption of methylene blue on fly ash
using the Freundlich and Langmuir isotherm models and found
the equilibrium data were represented well by the Langmuir isotherm equation. Hsu [46] reported that the adsorptions of Acid
Red 1 onto the raw and modified coal fly ashes could well fit the
Langmuir isotherm model. Moreover, the values of Q m increased
with increasing temperature and the adsorption capacity of both
fly ash types at 35 C were significantly higher (p < 0.05) than those
at other temperatures.
3.4. Adsorption kinetics
Kinetics experiments were carried out to study the effect of
contact time on SHA adsorption by modified fly ash. At the early
stage, the adsorption amount would increase as time elapsed.
The difference between SHA distribution in aqueous and solid
phases could be the driving force for the transfer of SHA to fly
ash surface. The approximate equilibrium of adsorption could be
established at later stage. The available sites on either acid- or
microwave-modified fly ash are limited. Once the vacant
adsorption sites on treated fly ash are occupied, it will be difficult
for continuing further adsorption of SHA, resulting in an equilibrium state for adsorption process. To better understand the kinetic
mechanism for the adsorption of SHA on modified fly ash, pseudofirst-order and pseudo-second-order kinetic models were used to
analyze the kinetic data. The linearized forms of pseudo-firstorder and pseudo-second-order models are shown in following
equations, respectively [47]:

lnQ e  Q t ln Q e  k1 t

t=Q t 1=k2 Q 2e t=Q e

where t is the contact time (min); Qt is the quantity of SHA adsorbed


at time t; k1 (min1) is the first-order equilibrium rate constant; k2
[g/(mg min)] is the second-order equilibrium rate constant. The
pseudo-first-order model is usually applied based on the assumption that the sorption of organic molecules on solid phase can be
considered as a reversible process with equilibrium being established. In pseudo-second-order model, the rate-limiting step is
regarded to be chemical adsorption involving adsorption force
through sharing or exchanging electrons between adsorbent and
adsorbate. Both of these two models have been widely used in
the analysis of adsorption characteristics.
The calculated parameters based on pseudo-first-order and
pseudo-second-order kinetic models are shown in Table 5. For both

Table 4
Adsorption parameters obtained from Freundlich and Langmuir isotherm models9.
Adsorbent

Freundlich parameters

Langmuir parameters

KF/(L/g)

Shand-treated A
Shand-treated B
BD-treated A
BD-treated B

K L /(L/g)

Qm/(mg/g)

15 C

25 C

35 C

15 C

25 C

35 C

15 C

25 C

35 C

15 C

25 C

35 C

7.396
7.932
10.368
11.082

12.376
13.425
14.672
14.893

91.355
93.461
17.196
17.849

1.679
1.722
2.057
2.160

1.705
1.853
2.395
2.407

2.737
2.928
2.726
2.773

0.032
0.041
0.027
0.038

0.088
0.102
0.068
0.082

0.164
0.179
0.081
0.097

283.42
304.56
66.38
70.49

321.84
366.95
92.69
104.53

378.51
392.07
117.93
132.25

269

C. An et al. / Fuel 165 (2016) 264271


Table 5
Kinetic parameters for adsorption of SHA on Shand and BD fly ash.
Pseudo-first-order parameters
Qe (mg/g)

Shand-treated A
Shand-treated B
BD-treated A
BD-treated B

Pseudo-second-order parameters
1

k1 (min

Qe (mg/g)

k2 [g/(mg min)]

15 C

25 C

35 C

15 C

25 C

35 C

15 C

25 C

35 C

15 C

25 C

35 C

168.83
224.69
27.88
30.94

229.27
283.93
37.36
42.81

267.54
308.15
46.92
51.77

0.08
0.09
0.05
0.09

0.14
0.22
0.17
0.15

0.31
0.28
0.18
0.19

215.58
264.86
41.89
44.49

278.97
325.48
52.27
56.08

317.32
349.50
63.72
69.39

0.003
0.004
0.005
0.003

0.005
0.006
0.006
0.008

0.005
0.009
0.008
0.014

treated Shand and BD fly ash, the fitting to pseudo-second-order


kinetic model possessed the higher correlation coefficients
(0.9320.994) than those for pseudo-first-order model (0.865
0.946). It suggests that the kinetic process about SHA adsorption
on modified fly ash can be better described by the pseudosecond-order kinetic model. At the same temperature, the order
of Qe for pseudo-second-order kinetic model decreases as follows:
Shand-treated B > Shand-treated A. The similar trend for different
BD fly ash types can be also found. In addition, different Qe values
can be found at different temperatures. The higher Qe values can be
obtained at 35 C when compared with those at 15 and 25 C.
These results consist with those obtained in isotherm study. The
kinetic process for the adsorption on fly ash was also investigated
in previous studies. In the adsorption of Congo red using calciumrich fly ash, it was found that the adsorption process could well
obey the pseudo-second-order kinetic model [48]. Similarly,
ztrk and Kavak [22] compared the pseudo-first-order and
pseudo-second-order kinetic models and showed that the latter
model showed better performance in describing the data for the
adsorption of boron on fly ash.
In the present study, better fitting results derived from pseudosecond-order adsorption mechanism indicate the adsorption
appears to be controlled by the chemisorption process. It was
reported that humic acid can interact with mineral surface via
ligand exchange [49]. In the adsorption process, aluminosilicate
in fly ash can provide surface hydroxyl sites while SHA molecules
contain carboxylic acid group. The adsorption of SHA on fly ash
can therefore occur through the interaction of ligand exchange.
Although the modification processes through acid or microwave
treatment are different, chemisorption can play important role in
the adsorption of SHA on both of these two different modified-fly
ash types.

The influence of ionic strength on adsorption process has been


observed in some previous studies [51]. Peng et al. [52] observed
that an increase in ionic strength resulted in the increasing adsorption of humic acid on montmorilloniteCu(II)/Fe(III) oxides magnetic material. Wu et al. [53] also reported that the adsorption of
organic dye on the mesoporous hybrid xerogel could be positively
influenced by the increasing ionic strength. For the adsorption of
SHA on modified fly ash, however, a different trend was observed
in which the increase of NaCl would result in decreasing removal
efficiency. The interactions between salts and organic compounds
can influence the adsorption performance. When there is attractive
electrostatic force between the adsorbent surface and adsorbate
ions, an increase in ionic strength can lead to the decrease of
adsorption capacity. Conversely, an increase in ionic strength can
enhance adsorption when the electrostatic attraction is repulsive

100

(a)

Shand-treated B

90
85
80
75
70
65
60
0

0.1

0.2

0.3

0.4

Ionic strength (mol/L)

3.5. Effect of ionic strength


100

(b)

BD-treated A

BD-treated B

95

Removal efficiency (%)

Oilfield wastewater is often characterized by high salt concentrations [50]. To better evaluate the adsorption performance of
modified fly ash, the effect of ionic strength on adsorption of SHA
on modified fly ash was investigated and the results are shown
in Fig. 3. For the electrolyte such as NaCl, the ionic strength is equal
to its concentration. The results showed the change of ionic
strength could affect the adsorption process. When the ionic
strength reached 0.1 mol/L, a highest removal efficiency of
79.91% and 93.56% could be obtained for Shand-treated A and
Shand-treated B, respectively. As the ionic strength in aqueous
solution further increased, the efficiency for the removal of SHA
would decrease correspondingly. When the ionic strength was
0.4 mol/L, the lowest removal efficiency of 71.62% and 86.37%
could be obtained for Shand-treated A and Shand-treated B,
respectively. Within the ionic strength range used in the current
study, the efficiency for SHA removal by Shand-treated B fly ash
was significantly higher (p < 0.05) than that by Shand-treated A
fly ash. There was a similar trend for the SHA adsorption on BD
fly ash at different ionic strength levels.

Shand-treated A

95

Removal efficiency (%)

Adsorbent

90
85
80
75
70
65
60
0

0.1

0.2

0.3

0.4

Ionic strength (mol/L)


Fig. 3. Effect of ionic strength on adsorption of tannin onto modified (a) Shand and
(b) BD fly ash.

270

C. An et al. / Fuel 165 (2016) 264271

[47]. There was the electrostatic attraction between the positively


charged fly ash surface and the negative SHA molecules. Salt can
diminish the electrostatic interaction of opposite charges of the
surface and the organic adsorbate. As ionic strength increased,
the adsorbed amount of SHA would decrease. Similar results have
been also observed in some previous studies [54].
4. Conclusions
This study investigated the performance of modified fly ash for
removing SHA from aqueous solution. Acid- and microwaveassisted treatments can lead to the increasing adsorption capacity
of fly ash. The different factors on the modification would have different contribution to the enhanced capacity. pH was the most critical factor which could influence the adsorption performance of
treated fly ash. SHA removal efficiency increased with the modified
fly ash dosage up to a certain limit and then it would reach a constant level. Langmuir isotherm could better fit equilibrium data for
the adsorption of SHA on modified fly ash. Kinetic analysis results
showed this process could be well described by pseudo-secondorder model. There was higher adsorption capacity at higher temperature and the adsorption of SHA on fly ash could be positively
influenced by an increase of temperature. The aqueous chemistry
such as ionic strength also had influence on the adsorption
performance.
The results presented the potential of modified fly ash as a suitable adsorbent for the removal of organic pollutants from oilfield
wastewater. The analysis helped to establish appropriate isotherm
and kinetic models to describe the interactions at water-fly ash
interface. The removal efficiency through adsorption on modified
fly ash can be also influenced by aqueous chemistry in the system.
The results can help understand the migration patterns of organic
pollutants in fly ash-water interface. The influencing parameters
gained from the current study can be used for the design and optimization of pilot treatment system. This study can help formulate a
sustainable development strategy for both oil and power industries. Further study is also needed to help obtain more theoretical
foundation for the interactions of oilfield pollutants and fly ash
characteristics. Different fly ash types and optimal design for treatment system will be also investigated for scale-up application.
Acknowledgments
This research was supported by the Natural Science Foundation
(51309096), the Program for Innovative Research Team in University (IRT1127), the 111 Project (B14008), the Natural Science and
Engineering Research Council of Canada and Petroleum Technology
Research Centre of Canada. We are thankful to SaskPower for providing the fly ash samples. The authors are also grateful to the editors and the anonymous reviewers for their insightful comments
and suggestions.
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