Materials and Design 116 (2017) 666675

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Materials and Design

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A novel approach to extract SiO2 from y ash and its considerable

adsorption properties
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'an 710119, Shaanxi, China
b
Key Laboratory of Coal Science and Technology, Ministry of Education and Shanxi Province, Taiyuan University of Technology, Taiyuan 030024, 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

A HAc/NaOH/ultrasonication-assisted
joint process was applied to extract
SiO2 from FA.
This joint process was feasible to sepa-
rate Si/Al effectively.
High purity (98.65%) and high yield
(51%) of SiO2 were obtained.
The extracted SiO2 exhibited better ad-
sorption prospect to dyes.
This research extended the application
and recycling of FA solid waste.

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

Article history: Silica extracting from y ash (FA) becomes a key technology for its comprehensive utilization of waste. Here,
Received 1 September 2016 high-purity SiO2 was extracted from FA via organic acid/inorganic alkali/ultrasonication-assisted joint process
Received in revised form 9 December 2016 and characterized by scanning electron microscopy, transmission electron microscopy, Brunauer-Emmet-Teller,
Accepted 10 December 2016
X-ray uorescence spectroscopy, X-ray diffraction, and X-ray photoelectron spectroscopy. The optimal extracting
Available online 15 December 2016
conditions were optimized: with acetic acid (HAc) leaching at 25 C for 1 h and FA/HAc of 1:3; then with 15%

Corresponding authors.
E-mail addresses: hzmachem@snnu.edu.cn (Q. Ma), hzmachem@snnu.edu.cn (H. Ma).

http://dx.doi.org/10.1016/j.matdes.2016.12.028
0264-1275/ 2016 Elsevier Ltd. All rights reserved.
 M. Gao et al. / Materials and Design 116 (2017) 666675
Keywords: NaOH dissolution at 100C for 2 h and FA/15% NaOH ratio of 1:4.5; cooled and introduced water (5.42 g/100 mL);
Fly ash ultrasonication-assisted for 20 min. The nal yield and purity of SiO2 were 51% and 98.65%, respectively. This
Extract joint method could be applied in several various FA raw materials and the extracted SiO2 exhibited better adsorp-
SiO2
tion prospect to cationic dyes of methylene blue and malachite green, which extended the application and
Adsorption
Dye
recycling of FA.
1. Introduction
Fly ash are widely used in cementitious products [1,2], construction
areas such as highway road bases [3], and efcient sorbents for removal
of heavy metals, organics and dyes from water [4]. However, despite so
many positive uses, the rate of production of FA is much larger than its
consumption. There are lots of coal-red power plants situated in the
place where disposal sites are difcult to choose. So the limited avail-
ability of space requires very strict management to satisfy related regu-
latory bodies. Moreover, FA has negative effect on the environment. The
disposal of FA is a more signicant problem than ash produced from
burning of municipal solid wastes because of its volume. So disposal di-
rectly of FA into the environment should be prohibited [5].
FA, usually with hollow sphere and activated sites, the main compo-
nents are silica, alumina, ferrous oxide, calcium oxide and varying
amounts of carbon and smaller amounts of other elements [6,7]. So
extracting silica from FA could not only realize comprehensive utiliza-
tion of FA to solve all kinds of negative issues brought about by FA, but
also extend the production of silica [8]. Moreover, it can also decrease
the Si/Al ratio in FA and realize silica and alumina separation. To im-
prove aluminum extraction efciency, a two-step acid leaching process
was applied to dissolve aluminum and aluminum-bearing crystals with
sulfuric acid, and N97% aluminum dissolving were obtained [9]. More-
over, the leaching process produced lots of by-products, sodium silicate
solution and amorphous silicon dioxide, which contained nearly all the
silicon from the coal ash. The response surface methodology was used to
optimize the extraction conditions of silica and alumina from FA, the ex-
tracts containing Si and Al ions were successfully converted to zeolites
by hydrothermal treatment at 95 C for 72 h [10].
Currently, some researches have been reported in the silica enrich-
ment and preparation for various forms of silicon products from FA.
Acid methods [1113] have been widely investigated. Typically, FA
has been dissolved using inorganic acid solvent (such as HCl or
H2SO4) to get aluminum salt solution at certain conditions, in this
step, SiO2 and Al2O3 have been separated roughly, then a series of sub-
sequent processing has been followed and SiO2 and Al2O3 have been pu-
ried. Drieux et al. [14] mixed the grinding FA and hydrochloric acid at
certain temperature, then roasting ground to separate Si and Al to get
highly puried SiO2 and Al2O3 simultaneously. However, large amount
of waste acid in the cyclic process were produced, which was harmful
to the environment. Alkaline methods [15,16] included limestone
sintering process, lime soda sintering process and alkaline dissolving.
FA was treated with alkaline cosolvent or direct alkali solution to realize
the separation of Si/Al. Wu et al. [17] studied the dissolution of
silicon and aluminum from FA at different conditions and the results
showed that 29.33% dissolution rate of SiO2 was obtained at 950 C
with 23 mol/L alkali, and digesting at 120130Cwith pressing. Si and
Al were separated preliminary, with low SiO2 productivity more com-
plex process and difcult administration. Acid/alkali combination meth-
od have attracted more attention [18,19]. Wu et al. [20] prepared high-
purity Al2O3 and superne SiO2 (99.5%) with acid/alkali process. The
consumption of acid and alkali and waste emission in the process
were limited and the energy consumption was high. In addition, ammo-
nia sulfate and calcination were also used to activate the non-reactive
substance for extracting the silica [2125]. Park [23] used the ammonia
sulfate to extract the high concentrated silica from FA with low temper-
ature sintering method and the recovery percentage of aluminum can
667
2016 Elsevier Ltd. All rights reserved.
reach 94.36%. Jin et al. [24] studied the phase transformation of calcina-
tion products of FA and sulfate. But there were some disadvantages,
such as large amount of FA residue, complex process and equipment,
which limited its application for industrialization [25]. Moreover, sever-
al authors prepared SiO2 nanostructures or xerogels with the organic
acid. Arenas et al. [26] synthesized silica xerogels with high surface
area using acetic acid as catalyst, and the inuence of acetic acid on
the pore structure and surface area of silica prepared by the sol-gel
method was investigated. Elsagh [27] synthesized silica nanostructures
and optimized the synthesis conditions, and the effect of molar ratio of
reactants including acids and silica pre-matter was studied. However,
the research was few and limited, and the above formation of SiO2 all
used organic precursors such as tetraethyl orthosilicate.
In view of the above shortcomings of traditional extraction method,
here we studied the preparation of high-purity and ne-grained SiO2
from inorganic precursor FA, a kind of solid waste residue, inorganic alka-
li/inorganic alkali/ultrasonication-assisted joint process rstly. The struc-
tural and morphological properties of SiO2 were investigated by scanning
electron microscopy (SEM), transmission electron microscopy (TEM),
Brunauer-Emmet-Teller (BET), X-ray uorescence spectroscopy (XRF),
X-ray diffraction (XRD), and X-ray photoelectron spectroscopy (XPS).
The effect of acid type, HAc dosage, acid leaching temperature, alkali dis-
solution temperature, and NaOH dosage on the purity and yield of SiO2
were systematically investigated. The universality of this joint method
was also investigated with various FA raw materials. On one hand, this
method had some advantages: less consumption of materials (acid-
base), low energy consumption with mild temperature, low cost with
simple equipment and operation, and high purity of product. On the
other hand, organic acid (acetic acid, HAc) was used in the process As a
frequently used non-toxic acid, HAc can be removed facilely from the re-
action system by calcined treating. Meanwhile, ultrasonication-assisted
process was also studied in the extracting of SiO2. Moreover, its adsorp-
tion capacities in dye removal from wastewater were studied. Consider-
ing the negative charged surface of the fresh prepared SiO2, two basic
dyes with cationic dominant groups, methylene blue (MB) and malachite
green (MG) were chosen as model pollutants in the experimental ad-
sorption test, the removal efciencies at different conditions were evalu-
ated. The possible adsorption mechanism was also proposed.
2. Experimental
2.1. Materials
The starting adsorbent material, raw FA, was collected from the
electro-lters from two power plants located in Shaanxi Province. Raw
FA was grinding fully for 10 min using a laboratory Plenary Rapid Grind-
ing Miller (XM-4, Minsks, China), then sieved using standard sieves of
30 m evenly with a ne grained particle size. All the organic acids
and other reagents were analytical grade and used without any further
purication. Distilled water was used throughout.
The chemical structures of MB and MG were displayed in Table 1.
2.1.1. Acid leaching step
FA was mixed with inorganic acid (HCl) or organic acid (HAc, oxalic
acid, or citric acid) in a mass ratio 1:3, then transferred it into a temper-
ature-controlled reaction kettle with a function of adjusting the temper-
ature at 25 C for 1 h with constant stirring. Then the mixture was
 668 M. Gao et al. / Materials and Design 116 (2017) 666675

Table 1 mi
Chemical structures, molecular weight and max of MB and MG. is
Dyes Chemical structure Molecular weight max (nm)

MB 319.85 665

MG 364.92 616.9

ltered and the residue was washed with distilled water several times, the mass of the components except SiO2, m1 is the mass of extracted
and dried, to obtain HFA. SiO2, mo is the mass of raw FA, w% is the percentage of SiO2 in raw FA.

2.1.2. NaOH alkali dissolution and ultrasonication-assisted step
The HFA was dissolving with 15 wt% sodium hydroxide solution
(1:4.5) and kept at 100 C for 2 h, then ltered. The resulting sodium sil-
icate solution was transferred to silica hydrosol by adjusting pH to 67
with HAc solution with ultrasonication-assisted process as Eq. (1)
shown. After gelation dehydrogenation, dried and obtained white
powder SiO2.
Na2 SiO3 2H H2 SiO3 2Na
The extraction of SiO2 was summarized in Scheme 1.
The main compositions of all samples (purity (P%) and yield (Y%))
were evaluated by XRF, and calculated by Eqs. (2) and (3):
X
P % 1 mi %
i1
m1
Y% % 3
m0  w%
2.2. Analysis and characterization
Scanning electron microscopy (SEM, TM3030, Hitachi) and trans-
mission electron microscopy (TEM, JEM-2100, JEOL) images were ob-
tained to analyze the surface morphology of all products. The chemical
and elemental compositions of FA samples were determined by means
of energy dispersive spectroscopy (EDS, high vacuum, Quanta 200, FEI
Corporation). The chemical compositions or purity of SiO2 samples
1 were determined by means of X-ray uorescence spectroscopy
(XRF 1800, Shimadzu corporation, Japan). And crystallinity and phase
composition of the powder was measured by an X-ray diffraction ana-
lyzer (XRD, D/Max2550VB+/PC, Japan).
N2adsorption/desorption isotherms was measured with a Physical
Adsorption meter (ASAP2020, Mike, USA) at liquid nitrogen tempera-
2 ture (196 C). The Brunauer-Emmett Teller (BET) method was used
to calculate the specic surface area using the adsorption data acquired
at a relative pressure (P/P0) range 01.0.
X-ray photoelectron spectra (XPS) were obtained from X-ray photo-
electron spectroscopy (AXIS ULTRA, Kratos Analytical Ltd.) equipped

Scheme 1. Synthesis of SiO2 from FA.

 M. Gao et al. / Materials and Design 116 (2017) 666675
with amonochromatic Al K X-ray as the excitation source.
2.3. Batch adsorption test
Batch adsorption experiments were conducted at room tempera-
ture. Typically, a certain amount of synthetic SiO2 white powder was in-
troduced into dye solution of MB or MG under mechanical stirring
(100 rpm) at original pH (6.8 for MB; 7.9 for MG) for various intervals.
At the predetermined time intervals, SiO2 was removed from the solu-
tion and dye concentration in the solution was then determined by
measuring the absorbance of the solution at max, using a UVvis spec-
trophotometer (UVT6, Beijing Purkinje General Instrument Co. Ltd.,
China). And the removal efciency of dye can be calculated according
to the references [28,29].
2.4. Elution and reuse test
Elution of dyes from SiO2 was carried out in 50 mL alcohol and dis-
tilled water (1:1 in volume) for 30 min with stirring at 100 rpm and
25 C. The nal concentration of dyes was determined as Section 2.3
stated. In order to study the reusability, consecutive and elution cycles
Fig. 1. SEM (a) FA; (b) extracted SiO2 and (c) TEM images of SiO2.
669
were repeated for 5 times in same conditions.
3. Results and discussion
3.1. Characterization of the extracted SiO2
3.1.1. Compositions and phase
The XRD patterns of raw FA and prepared SiO2 samples are shown
in Fig. S1. The main composition of raw FA was SiO2 [30], identied by
the sharp peaks at 2 = 22.1 and 25.4, along with small amounts
of Al2O3 (2 = 40). The result implied that SiO2 in the raw FA
mainly existed in crystal shape. However, the obtained silicate material
SiO2 from FA was amorphous for the weaker wide peak at 2 = 22.6
[31,32].
The composition of synthesized silica material was also investigated
by EDS (Fig. S2). The raw FA consisted of Si and Al primarily while the
contents of Al decreased signicantly and increased contents of Si
were detected in the extracted SiO2 [33].
670 M. Gao et al. / Materials and Design 116 (2017) 666675

Fig. 2. XPS spectra for the extracted SiO2: (a) survey; (b) O 1s; (c) Si 2p.

[34]. A smooth and spherical morphology was detected for raw FA,
3.1.2. Morphology of synthetic SiO2 while uniform dense microstructure and signicant abundant porous
To gain the real morphology of samples, SEM and TEM were used to network structure were demonstrated for the SiO2 extracted from FA
determine the qualitative and morphological characteristics (Fig. 1) [35]. TEM images showed that the morphology of SiO2 powder was
 M. Gao et al. / Materials and Design 116 (2017) 666675 671

homogeneous and almost spherical, and the particles dispersed well

and connected with each other [36].

3.1.3. Textural properties

The N2adsorption-desorption isotherms and pore size distribution of
SiO2 are given in Fig. S3.The type IV isotherms with apparent hysteresis
loops were observed [37]. As shown, the quantity of N2 adsorption in-
creased sharply at a relative pressure P/P0 of 0.8, conrming the capil-
lary condensation of N2 within the primary mesopores. And specic
surface area and pore volume of SiO2 might be benet (32.8 m2/g;
10.1 cm3/g) for the possible adsorption, and more precise reason
would be further studied. Moreover, a primary particle size distribution
centered at around 20 nm was observed, indicating the presence of de-
ned mesopores and dense structure [38].

3.1.4. XPS analysis

XPS was also employed to examine surface elements and their va-
lence states (Fig.2). From the survey spectra, the peaks of Si, C and O el-
Fig. 4. Effect of Tacid on the product distribution ((a) SiO2; (b) Al2O3; (c) Na2O) and yield of
ements were detected, showing Si and O were dominant, and high (d) SiO2.
purity of the products. A band at 285 eV was corresponding to C 1s for
C4 + species as the internal standard. The peak at 101.1 eV for Si 2p
was corresponding to Si4+ species, and 530.6 eV was corresponding to
O 1s for O2 species, respectively [39,40]. And only Si\\O bonding in the introduction of new impurities, compared to traditional inorganic
the symmetric peak was detected, suggesting that the elements in acid such as HCl. Based on above discussions, HAc was chosen in the fur-
SiO2 samples existed in the form of oxide mainly. ther research.

3.2. Optimization of SiO2 extracting conditions
3.2.1. Effect of acid type
The effect of acid and acid type (HCl, HAc, oxalic acid, and citric acid)
on the product distribution and the purity of SiO2 was studied (Fig. 3). A
high percentage of Na2O, Al2O3 and Fe2O3 were obtained for the SiO2 ob-
tained with direct NaOH dissolution in the absence of acid leaching, in-
dicated that the main components other than SiO2 in FA could not be
removed without acid treatment [41]. Compared to inorganic acid HCl
leaching, higher purity SiO2 (N96.8%) was obtained for all three organic
acids, suggesting that organic acids exhibited better leaching effect in
extracting silica from FA in the rst step. It may be due to that phase
transformation from oxides to soluble ions occurred during the leaching
process, thus impurities were removed with acid leaching. Moreover, as
a common organic weak monoprotic acid, it was safety and facile for
HAc in operation and cost [42,43]. Meanwhile, HAC could activate raw
FA fully with minor impurities and decompose completely without
3.2.2. Effect of acid leaching temperature Tacid
The effect of acid leaching temperature (Tacid) on the product distri-
bution and yield of SiO2was studied. As can be seen from Fig. 4, high pu-
rity (P% N 95%) of SiO2 was obtained and changed hardly with Tacid
varying from 20 to 90 C, and impurities in SiO2 were removed well.
However, the purity of SiO2 decreased obviously with temperature in-
creased further (Tacid N 90 C), probably due to the evaporation of HAc
at higher temperature, thus SiO2 could not be fully extracted for the dec-
rement of acid [44]. In addition, Tacid affected signicantly on the yield
(Y%) of SiO2. And two higher Y% peaks (40% and 37.55%) could be clearly
seen at 25 C and 80 C, respectively, indicated that lower or higher tem-
perature was unfavorable to remove impurities in the acid leaching,
maybe due to the leaching inefciency or volatilization of HAc [45]. So
considering the effects of P% and Y% of SiO2, Tacid in the rst step for
the preparation of SiO2 was selected at 25 C.
3.2.3. Effect of alkali dissolution temperature (Talkali)
The alkali dissolution temperature (Talkali) had a signicant inuence
on the purity and yield of SiO2 as Fig. 5 shown. The P% and Y% of SiO2 in-

Fig. 5. Effect of Talkali on the product distribution ((a) SiO2; (b) Al2O3; (c) Na2O) and yield of
Fig. 3. Effect of acid type on the product distribution. (d) SiO2.
 672 M. Gao et al. / Materials and Design 116 (2017) 666675
Fig. 6. Effect of HAc dosage on the product distribution ((a) SiO2; (b) Al2O3), yield of
(c) SiO2 and (inset) specic surface area of SiO2.
creased distinctly with the increasing of Talkali. The P% and Y% of SiO2
reached up to 97.5% and 38%, respectively at 100 C, suggested that
higher temperature improved the dissolution of silicon from HFA in
the full alkali dissolution reaction and the formation of hydrated silica
[46,47]. Moreover, lower percentage of impurities (b 20%), and higher
separation efciency (Si/Al about 4:1) were obtained at this tempera-
ture [48]. Considering the economic and feasibility, Talkali of 100 C
was chosen to be the optimal alkali dissolution temperature in the sec-
ond step.
3.2.4. Effect of HAc dosage
As shown in Fig. 6, no obvious changes of the purity of SiO2 was ob-
served with the increasing of FA:HAc ratio and a maximum P% of 98.7%
at FA:HAc = 1:3 was obtained [49]. While Y% of SiO2 was inuenced sig-
nicantly by the dosage of acid and Y% of SiO2 increased obviously with
the increasing of FA:HAc from 1:1 to 1:3, and then decreased sharply for
FA:HAc = 1:4 [50]. The specic surface area of extracted SiO2 showed a
continuously rising trend with the increasing of FA:HAc, and then in-
creased slowly when FA:HAc higher than1:3 (Fig. 6 inset). This sug-
gested that phase transformation of FA in a great degree happened
that contributed to the dissolution of SiO2 at the ratio of FA:HAc = 1:3
[51]. So FA:HAc = 1:3 was chosen as the optimal acid leaching
condition.
Fig. 7. Effect of NaOH dosage on the product distribution ((a) SiO2; (b) Al2O3) yield of (c)
SiO2 and (inset) specic surface area of SiO2.
Fig. 8. Effect of water volume on (a) purity, (b) yield and (inset)specic area of SiO2.
3.2.5. Effect of NaOH dosage
Little differences were observed for the dosage of NaOH on the puri-
ty of SiO2, 97.5% and 97.85% of P% were obtained at 1:2 and 1:4.5, re-
spectively. Y% of SiO2 increased with the increasing of NaOH dosage
and the highest Y% was obtained at FA:NaOH = 1:4.5 [52]. Moreover,
the surface area of SiO2 increased sharply with the increasing of NaOH
(Fig. 7 inset) [53]. This maybe attribute to the full dissolution of silicon
from SiO2 or other phases to Na2SiO3 under the ratio of 1:4.5. So 1:4.5
of HFA:NaOH was chosen in the further study.
3.2.6. Effect of water volume (VH2O)
After the alkali dissolution, distilled water was added, the volume of
water (VH2O) has a signicant decisive effect on the concentration of
Na2SiO3 in extracted solution (Fig. 8) [54,55]. A doublet curve relation-
ship of VH2O with the purity and the specic area was observed at
VH2O 50 and 100 mL, while the highest yield of SiO2 was obtained at
VH2O 100 mL.
At lower concentration (VH2O N 100 mL), a transparent sol could be
easily formed, while a white gel formed at higher concentration
(VH2O b 50 mL) precipitate and separation of SiO2 were difcult for
these stable systems, so VH2O of 100 mL was used in the further study
(Fig. S4).
3.2.7. Effect of assisted conditions
SiO2 formed by the reaction of Na2SiO3 and H+ [56], stirring or ultra-
Fig. 9. Effect of assisted methods on the purity of SiO2.
 M. Gao et al. / Materials and Design 116 (2017) 666675 673

Table 2 chased towards MG is shown in Fig. 10a. MG removal increased with the
The principle chemical compositions and yield of SiO2. increasing of dosage of adsorbents, and higher MG removal was ob-
Samples Compositions (%) Yield (%) of SiO2 served for prepared SiO2 than the purchased one, indicating the pre-
SiO2 Al2O3 Fe2O3
pared SiO2 exhibited better adsorption capacities. And the purchased
SiO2 mainly existed in crystal shape with larger particle size, identied
FA-1 49.1807 35.1335 3.5806 51.97
by the sharp narrow peak at 2 = 25.4. The prepared SiO2 was amor-
FA-2 47.6197 17.7306 14.7790 45.67
SiO2-1 98.6515 0.9734 0.3752 / phous with smaller size that was benecial for the adsorption, and the
SiO2-2 97.9705 1.2823 0.4209 / primary particle size distribution centered at around 2.8 nm with few
mesopores by BET test. This is probably due to the contribution of the
functional group of\\OH on its surface and uniform ne grained of pre-
sonic can facilitate mass transfer and the generation of SiO2, so the effect pared SiO2. Moreover, the specic area of the purchased SiO2 was
of the assisted methods (ultrasonic, stirring and stewing) on the purity 0.59 m2/g, much smaller than the prepared one (32.8 m2/g), However,
of SiO2 was investigated (Fig. 9). The highest P% (98.65%) was obtained this value was much lower than other techniques reported [59,60].
for ultrasonic-assisted method. It may be due to that ultrasonication However, from the environmentally friendly point of view, this method
most promoted the uniformity of the reaction system and SiO2 should have potential application in future.
formation.
Considering of the uniform morphology of the extracting product, 3.4.2. Adsorption property of prepared SiO2
and its purity and yield, the conditions for extracting SiO2 from FA was
optimized: HAc leaching at 25C for 1 h at FA/HAc of 1:3; then 15% 3.4.2.1. Effect of adsorbates. The adsorption capacities of the prepared
NaOH dissolution at 100 C for 2 h at FA/15%NaOH of 1:4.5; water vol- SiO2 to MG and MB are shown in Fig.10b. The removal efciencies (R
ume 100 mL; ultrasonication-assisted for 20 min, the highest yield (%)) for both adsorbates increased with the dosage of SiO2 increasing,
(51%) and purity(98.65%) of SiO2 were obtained. and eventually reached saturation/equilibrium adsorption and the max-
imum adsorption value. And the highest removal efciencies (N99.8%)
3.3. Universality of the joint extraction method of both dyes were observed with 1000 mg/L prepared SiO2 within
80 min. This probably ascribed to electrostatic interactions between
To verify the feasibility and universality of this joint method, it the cationic dyes and the deprotonated \\OH of SiO2 skeleton [61]
was applied into two other raw FA materials (FA-1, FA-2) principal (Scheme 2), which also conrmed by FT-IR spectra. The peak at
chemical compositions of these two raw FAs were SiO2, Al2O3 and 3412 cm1 of Si\\OH decreased even disappeared after adsorption, in-
Fe2O3 as Table 2 shown [57,58]. The purities of extracted samples dicating the interaction of-OH and the adsorbate. Moreover, the number
SiO2-1 and SiO2-2 reached up to 98.65% and 97.97%, respectively indi- of silicon hydroxyl on the surface of SiO2 decreased obviously after ad-
cated that this HAc/15% NaOH/ultrasonication-assisted joint process sorption according to the theory of acid-base titration [62]. In addition,
for extracting SiO2 from FA was feasible and universality. bigger roughness and surface area of SiO2 also promoted the adsorption
of dye.
3.4. Adsorption properties tests
3.4.2.2. Effect of contact time on dyes removal. The adsorption of MG and
3.4.1. Comparison of SiO2 prepared and purchased MB on SiO2 at initial concentration of 50 mg/L and 25 C was studied as a
A comparison of adsorption capacities of SiO2 prepared and pur- function of time to determine the optimal contact time. MG removal

Fig. 10. Effect of parameters on dye removal by prepared SiO2: (a) adsorbents; (b) adsorbates; (c), (d) contact time.
674 M. Gao et al. / Materials and Design 116 (2017) 666675
Scheme 2. Possible interaction between dyes and prepared SiO2.
increased signicantly with contact time prolonging, and then in-
creased slowly until the highest removal efciency (99.9%) was obtain-
ed at 3 h (Fig. 10c). Compared to the adsorption of MG, the adsorption of
MB was much faster and its removal increased sharply at the initial
100 s(Fig. 10d), and then increased slowly on the whole and the highest
removal efciency (99.7%) was obtained at 500 s. The adsorption rate
inuenced by intraparticle diffusion is faster than that of mass transfer,
this result suggested that the adsorption process of MG inuenced by
the mass transfer, while the adsorption of MB inuenced by the
intraparticle diffusion [63,64]. Moreover, MB was not dimerized at
lower concentration of 50 mg/L (max = 665 nm for single dimer;
max = 661 nm for dimer) [65]. On the contrary, MG tended to degrade
at higher alkaline pH, at this initial pH(7.9), MG not inuence by auto-
degradation function.
3.4.2.3. Recycle of the extracting SiO2. The recycle of the adsorbent is a key
factor in improving adsorption process cost [66]. As shown in Fig. 11,
slight decreasing in adsorption properties and relative higher removal
efciencies of the cationic dyes were obtained even after 5 cycle
(99.7% to 78.9% for MG; 99.3% to 76.5% for MB) [67], suggesting that
the synthesized material SiO2 be regenerated and reused in multiple ad-
sorption-desorption cycles well.
4. Conclusion
In this paper, high purity (98.65%) and ne-grained SiO2 with satis-
factory total yield (51%) through organic acid/inorganic alkali/
ultrasonication-assisted joint process was extracted effectively from
FA. Physical properties and purity of prepared SiO2 were studied by
Fig. 11. Recycle of prepared SiO2 on dyes removal.
SEM, TEM, BET, XPS and XRF. And this joint extracting method of SiO2
from FA was feasible and extensive used in several kinds of FA materials.
Moreover, the prepared SiO2 showed good adsorption capacity to the
cationic dyes MG and MB. The result showed that the procedure of
high purity SiO2extracting from FA proved to be simple, efcient and en-
vironmentally friendly. More importantly, it contributed to achieve the
aim of waste control by waste and extend the application and recycling
of FA.
Acknowledgments
The authors are grateful to be supported by the Natural Science
Foundation of Shanxi Province (no. 2015021107).
Appendix A. Supplementary data
Supplementary data to this article can be found online at http://dx.
doi.org/10.1016/j.matdes.2016.12.028.
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