Journal of Analytical and Applied Pyrolysis 137 (2019) 96–105

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Journal of Analytical and Applied Pyrolysis

journal homepage: www.elsevier.com/locate/jaap

Solid waste to biofuels and heterogeneous sorbents via pyrolysis of wheat T

straw in the presence of fly ash as an in situ catalyst
Lihui Gaoa,b,c, , Jillian L. Goldfarbb,c,d
⁎

a
School of Chemical Engineering and Technology, China University of Mining and Technology, Xuzhou, 221116, People’s Republic of China
b
Department of Mechanical Engineering, Boston University, 110 Cummington Mall, Boston, MA, 02215, United States
c
The Leone Family Department of Energy & Mineral Engineering, The EMS Energy Institute, and The Institutes of Energy and the Environment, The Pennsylvania State
University, University Park, PA, 16802, United States
d
Department of Biological and Environmental Engineering, Cornell University, 226 Riley-Robb Hall, Ithaca, NY, 14853, United States

ARTICLE INFO ABSTRACT

Keywords: Solid waste disposal imposes worldwide environmental and economic hardships. To alleviate such issues, the
Wheat straw present work uses coal fly ash to in situ catalyze the pyrolysis of wheat straw, an abundant agricultural biomass,
Coal fly ash and to simultaneously produce heterogeneous sorbents for water treatment. Coal fly ash mixed in varying
Pyrolysis proportions with wheat straw shows a catalytic effect by lowering the temperature at which many non-
Biofuels
condensable gaseous species are released. As the weight fraction of fly ash in the wheat straw increased from 1 to
Heterogeneous biochar
10 wt%, the overall conversion of biomass increased. 1–5 wt% fly ash favored conversion to the gas phase
Catalyst
(especially CO2, CH4 and C2H4), whereas the 10 wt% mixture produced more condensable species with fewer
detectable oxygenated components and increased furan concentration. For a more complete waste-to-byproduct
transformation, the resulting heterogeneous wheat straw-fly ash biochars were used to removed methylene blue,
a model organic pollutant, from water, at higher capacities and faster rates than biochar alone. Overall, the coal
fly ash may be a potential inexpensive catalyst for in situ upgrading biomass pyrolysis, simultaneously producing
heterogeneous sorbents with enhanced adsorption capacities for organic pollutants.

1. Introduction The literature contains many examples of biomass conversion pro-

Given our limited global fossil fuel supply, increasing energy con-
sumption, and the anthropogenic impacts of energy use, considerable
attention is focused on the development of renewable fuels [1]. Biomass
is touted as a clean fuel feedstock as it has a negligible sulfur content,
yielding lower SO2 emissions than conventional fossil fuels and has po-
tentially net negative CO2 emissions [2]. Among biomass to energy
conversion technologies, thermochemical techniques such as pyrolysis
(heating in the absence of oxygen) offer the potential to produce liquid
fuels that could replace fossil fuels for power generation, in transporta-
tion applications, and could be used to produce valuable chemicals [3].
However, pyrolysis bio-oils have high viscosity and acidity, and high
water, oxygen and ash contents, all of which lead to unstable and cor-
rosive fuels [4]. Current upgrading processes for pyrolysis bio-oils in-
clude hydrodeoxygenation, catalytic cracking, emulsification and steam
reforming [5], but the poor quality, low yield and cost of upgrading
hampers the commercial application of pyrolysis bio-fuels [6,7].
cesses that use a downstream catalyst to up-convert evolving vapors
[8,9], and others that focus on in situ processes, whereby the catalyst is
added directly to the biomass [10,11]. In both approaches, natural and
synthetic aluminosilicates and solid acid catalysts can promote het-
erogeneous biomass conversion reactions to obtain deoxygenated che-
micals and fuels [12,13]. Among solid acid catalysts, montmorillonite
K10 exhibits catalytic activity for cellulose to levoglucosan pyrolytic
conversion [14], potentially due to montmorillonite’s dual Brønsted
and Lewis acid sites [15]; Brønsted acidity decreases with a corre-
sponding increase in Lewis acidity as temperature increases [16]. Re-
cently, our group demonstrated that bentonite clay can improve pyr-
olysis gas yield and bio-oil quality via in situ catalytic upgrading [17].
To improve the economic viability of pyrolytic biomass to biofuel
conversions, we must identify low-cost catalysts, including materials
that need not be recovered and recycled, such as coal fly ash.
Fly ash is produced by burning coal in power stations and other
industrial sources [18]. Every year over 100 million tons of fly ash,

⁎
Corresponding author at: School of Chemical Engineering and Technology, China University of Mining and Technology, Xuzhou, 221116, People’s Republic of
China.
E-mail address: gaolihui0709@126.com (L. Gao).

https://doi.org/10.1016/j.jaap.2018.11.014
Received 18 August 2018; Received in revised form 6 November 2018; Accepted 10 November 2018
Available online 15 November 2018
0165-2370/ © 2018 Elsevier B.V. All rights reserved.
L. Gao, J.L. Goldfarb Journal of Analytical and Applied Pyrolysis 137 (2019) 96–105

bottom ash, slag, and flue gas desulfurization products are generated, Table 1
much of which reside in containment ponds that pose environmental Proximate and surface area analysis of raw wheat straw and coal fly ash.
and health risks [19]. Coal fly ash is comprised of 60% to 80% clay Proximate Analysis Wheat Straw (Raw Biomass) Coal Fly Ash Average Wt %
minerals, with kaolinite, quartz and pyrite making up the majority [20]. Average Wt % (dry basis) (dry basis)
SEM-EDS shows that fly ash consists mainly of amorphous alumino-
silicate spheres and a lesser amount of iron-rich spheres [18]. As such, Volatile Matter 86.09 ± 0.79 11.00 ± 0.22
Fixed Carbon 9.27 ± 0.89 12.89 ± 0.06
coal fly ash contains natural catalysts such as iron oxide, lime, alkalis, Ash (Inorganic 4.64 ± 0.11 76.11 ± 0.20
alumina and has been suggested as a possible catalyst for carbonaceous Matter)
wastes such as biomass and plastics to biofuel conversions [19,21–23]. Ultimate Analysis
The present work investigates the suitability of fly ash as an in situ C 53.94 ± 0.56
H 5.93 ± 0.01
catalyst for the pyrolysis of wheat straw. Wheat straw was chosen as a
N 0.70 ± 0.09
target biomass as it is an abundant, inexpensive agricultural waste [24] O 39.32 ± 0.63
that requires significant pre-treatment to be combusted as a solid fuel to S 0.11 ± 0.01
remove high potassium and alkali contents that lead to slagging and
fouling [25]. However, wheat straw pyrolysis is potentially catalyzed Surface Area Analysis Wheat Straw (Raw Biomass) Coal Fly Ash
by the presence of such alkalis. To date, literature reports of wheat
SBET, m2/g 4.752 ± 0.202 30.146 ± 0.527
straw pyrolysis oils show mainly C2 to C10 compounds [26] with a large Vtotal,cm3 0.0095 ± 0.0009 0.0427 ± 0.0016
fraction of oxygenated and aromatic compounds, and at higher heating Vmeso,cm3 0.0081 ± 0.0008 0.0362 ± 0.0014
rates ketones and alcohols (including phenols) [27]. Wheat straw pyr-
SEM/EDS Wheat Straw Ash Average Coal Fly Ash Average Wt %
olysis could be further improved using coal fly ash in the biomass as an
Elemental Wt %
in situ catalyst. By using a slow pyrolysis technique (10 °C/min) we can Analysis
simultaneously produce a heterogeneous biochar sorbent material that
can remove a model organic pollutant from water, potentially con- Al 2.93 ± 3.18
verting these wastes to three sustainable products: pyrolysis gas, bio-oil, Ba 1.65 ± 0.08
Br 0.42 ± 0.07
and a water treatment material. C 31.94 ± 20.16
Ca 1.17 ± 0.01 1.38 ± 3.01
2. Experimental Cl 0.05 ± 0.05
Cr 5.02 ± 0.12
Cu 2.85 ± 0.04
2.1. Samples
Fe 9.35 ± 0.29 1.49 ± 2.64
K 2.82 ± 0.02 1.54 ± 3.65
Wheat straw (Thunder Acres, Kansas, USA) was ground in a coffee Mg 0.46 ± 0.77
mill and sieved to a particle size between 100 and 300 μm to limit Mn 0.05 ± 0.01
transport limitations by maintaining a Biot number less than 0.1 [28]. Na 4.94 ± 7.69
O 30.67 ± 13.53
Fly ash was obtained from a local utility company that uses a blend of P 0.49 ± 0.03
high-volatile bituminous coals with average higher heating values S 6.43 ± 0.65 2.36 ± 3.39
ranging from 22,000–28,000 kJ/kg in two 50 MW boilers. Particles Sc 2.78 ± 0.31
were all less than 150 μm in diameter, with the majority below 70 μm. Si 44.82 ± 2.31 8.48 ± 0.08
Sr 1.50 ± 0.01
Blends of the biomass and fly ash were measured on a semi-micro-
Ti 15.47 ± 0.54 12.39 ± 10.05
balance to the 0.1 mg, then vortex mixed to insure homogeneity. The Zn 2.31 ± 0.31
following abbreviation system denotes these mixtures throughout the V 1.70 ± 0.14
text: WS/FA(a:b) where WS is wheat straw, FA is fly ash, (a:b) is the
mass ratio (w/w).
2.2. Pyrolysis of biomass and biomass-coal ash blends
Proximate analysis was performed by thermogravimetric analysis
using a Mettler Toledo TGA-DSC1. Samples (raw biomass and later bio-
The TGA-DSC was used to determine the biochar yield and pyrolytic
char) were heated in the TGA under N2 to 110 °C at 50 °C/min and held
thermal decomposition behavior using approximately 10 mg samples,
30 min (to establish a dry baseline), then to 900 °C, held for 30 min
heated at 5 and 25 °C/min in high purity nitrogen flowing at 50 mL/min
under N2 (loss due to volatile matter), and finally to 950 °C at 50 °C/min
from 25 °C to 110 °C and held for 30 min to remove moisture, then
under air and held for 30 min (loss due to fixed carbon); residual mass is
heated from 110 °C to 800 °C under N2 at β and held for 30 min to
considered to be inorganic matter, loosely termed “ash.” Results are
exhaust all volatiles. A baseline run at each heating rate was used to
presented as the average of at least three runs with the corresponding
correct for buoyancy.
standard deviation. Ultimate analysis of the wheat straw was performed
To analyze the biofuel produced and the nature of the resulting
on a LECO 628 analyzer equipped with sulfur module for CHN (ac-
biochars, the raw biomass and biomass-coal fly ash blends (0.5-0.6 g)
cording to ASTM D-5373) and S (ASTM D-1552), with oxygen de-
were placed in a porcelain boat in a 2-MTI tube furnace as previously
termined by difference. A semi-quantitative elemental distribution of
described [29]. To determine an appropriate temperature for pyrolysis
the coal fly ash and wheat straw ash was performed via SEM-EDS on a
to compare the impact of blend ratio on biofuel quality, the WS/
Thermo Fisher (FEI) Q250 with gold sputter-coated samples; elemental
FA(20:1) mixture was heated at 10 °C/min in 120 mL/min of flowing
results are shown as the weight and atomic range and average com-
high purity nitrogen to a series of temperatures (450 °C, 550 °C, 650 °C,
position of 12 samples for coal ash and 5 samples for wheat straw ash to
750 °C) and held for 1 h. After analysis of these experiments, 650 °C was
explore the range of elemental compositions in the samples.
chosen as the pyrolysis temperature, and all blends were subsequently
The porous nature of the samples was determined using nitrogen
pyrolyzed at 650 °C at least twice each sample; results (including yields)
adsorption isotherms with a BELSORP-max version 2.1. Approximately
are averaged and if runs deviated by more than 5% they were repeated.
400 mg of each sample was degassed at 80 °C for 10 h under vacuum to
During pyrolysis in the tube furnace, the devolatilized gases were
remove any surface impurities. The surface area was measured via N2
measured online by a Quadrupole Mass Spectrometer Residual Gas
adsorption at 77 K via BET analysis using 11 data points over a partial
Analyzer (Extorr RGA XT300 M) monitoring m/z signals of 2, 16, 26,
pressure range of 0.05-0.35. Proximate analyses and surface areas of
27, 30 and 44, respectively (H2, CH4, C2H2, C2H4, C2H6, CO2) as a
raw materials are given in Table 1.

97
L. Gao, J.L. Goldfarb
Fig. 1. Derivative thermogravimetric curves for wheat straw and wheat straw + fly ash blends.
function of partial pressure using a Pirani gauge (for more information
on monitoring pyrolysis gas compounds, we refer the reader to Evans
and Milne [30], and Huang et al. [31]). Gas yield is quantified knowing
the total flow rate (controlled by an Omega Mass Flow Controller, ±
0.2 mL/min) and pressure from the Pirani gauge assuming the ideal gas
law applies. Condensable gases were trapped in 4 mL of di-
chloromethane at 4 °C (Acros Organics, HPLC grade). After pyrolysis,
the solid samples were cooled to room temperature under nitrogen to
prevent oxidation.
The condensable bio-oil components were analyzed on an Agilent
gas chromatograph (7890B) - mass spectrometer (5977 A) (GC–MS) in
split mode with a split ratio of 30:1. 1 μL samples were injected at
250 °C using helium (ultra-high purity,) as the carrier gas at a total flow
rate of 1 mL/min. The GC oven was initially set at 45 °C with a hold
time of 10 min, followed by heating at 3 °C/min to 250 °C and then held
for 5 min. The interface temperature was set to 325 °C. Mass spectra
were recorded under electron ionization mode within the m/z range of
29–300 from 7 to 80 min, with a 7-minute solvent delay. The GC–MS
was calibrated using biofuel “marker” compounds, which were chosen
as they are detected in biofuels from a variety of biomasses across the
literature. Each compound was calibrated with over 7 points between
10 and 700 ppm, with a minimum R2 value of 0.996. Additionally, the
chromatograph was semi-quantitatively analyzed by integrating the top
(by area) 20 gas chromatogram peaks. Peaks are reported with relative
area to the nearest calibrated compound if their NIST-library identifi-
cation similarity was greater than 90% and their identity compared to
prior compounds detected in the literature. Samples were analyzed at
least twice; errors were estimated by frequent (daily) injections of
known mixtures and are less than 5 ppm for every compound.
Compounds that were calibrated for are reported in Tables and Figures
as mgcompound/gbiomass; those that were semi-quantitatively analyzed via
chromatogram area are reported as total ion count (TIC)/gbiomass.
2.3. Evaluation of biochars’ sorption behavior
To determine the impact of co-pyrolysis on the relative adsorption
capacities and uptake rates of each biochar, we ran methylene blue
(MB) adsorption experiments. Batch adsorption experiments used a 1:
400 biochar : solution ratio at room temperature (25.5–27.0 °C). The
adsorption isotherms were performed with MB solution concentrations
of: 20, 50, 80, 100, 150, 200, 250 mg/L and allowed to equilibrate for
48 h. Adsorption kinetics were determined using an 80 mg/L MB solu-
tion and sampled at time intervals of 1, 2, 5, 10, 20, 30 min, and 1, 2, 4,
6, 8, 24 h. Samples were centrifuged for 1 min and the dye concentra-
tions were determined by a UV–vis spectrophotometer (Shimadzu UV-
1800) at 664 nm calibrated using 13 points over a concentration range
98
Journal of Analytical and Applied Pyrolysis 137 (2019) 96–105
of 0–15 mg/L to an R2 value of 0.99995 (where Beer-Lambert law ap-
plies for this compound). All experiments were performed in duplicate
and the average values are reported.
The adsorption equilibrium experimental data were fit to Langmuir
(Eq. (1)), and Freundlich (Eq. (2)) isotherms to relate Ce and qe, the
equilibrium concentrations of adsorbate in solution and on adsorbent
surface, respectively.
qmKLCe
Langmuir : qe =
1 + KLCe (1)
Freundlich: qe = KF Ce1/ n (2)
qm and KL are the maximum adsorption capacity and equilibrium
constant of adsorption associated with complete monolayer coverage;
KF indicates adsorption capacity, with 1/n representing the hetero-
geneity factor. Data from kinetic experiments were fit to pseudo-first
and second-order models to assess the mechanism(s) controlling the
overall rate of adsorption and determine rate constants (k) as a function
of qe and adsorption at time t, qt.
dq
Pseudo first order: = k1 (qe qt )
dt (3)
dq
Pseudo second order : = k2 (qe qt ) 2
dt (4)
3. Results and discussion
Table 1 details the characteristics of the raw biomass and wheat
straw. There is a considerable amount of residual pyrolyzable matter
(11 wt%) left in the coal fly ash. Elemental analysis shows the fly ash is
a heterogeneous mixture of potentially catalytic materials such as Na,
Mg, Mn, etc. as is often observed throughout the literature [18]. As
shown in the DTG curves of Fig. 1, there was minimal difference ob-
served in the peak devolatilization temperatures for the wheat straw
(WS) and WS + fly ash (FA) blends. As suggested by ICTAC Kinetics
Committee recommendations for thermal analyses, the peak reaction
rate scales with heating ramp rate (a difference of 5 times faster de-
composition at peak temperature, which shifts from ∼ 590 K to 615 K
in going from 5 to 25 °C/min), as can be seen in the y-axis scales of
Fig. 1 [32]. This suggests minimal change in the overall rate of con-
version of the pure versus “catalyzed” biomass. Such a finding is not
uncommon; Nowakowski et al. found a decrease in volatiles produced
for K-impregnated short rotation willow coppice biomass and an in-
crease in activation energy, with a similar decrease in volatile yield but
a decrease in activation energy for a synthetic biomass mixture
L. Gao, J.L. Goldfarb Journal of Analytical and Applied Pyrolysis 137 (2019) 96–105

Table 2
Product yields (total solid, gas and liquid phases) for pyrolyzed samples as a function of starting sample mass (WS + FA) and on a per biomass yield (WS only) ± one
standard error.
Sample Wt % Pyrolysis Solid Yield (wt%) Gas Yield (wt%) Liquid Yielda (wt%) Solid Yield Gas Yield Liquid Yielda
Biomass Temperature (°C) (wt%) (wt%) (wt%)
Total Product Distribution [per mass sample Biomass Product Distribution [per mass
(WS + FA) basis] biomass (WS only) basis°]

Pyrolysis Temperature Experiments

WS_FA(20:1) 95 450 32.0 ± 0.1 19.0 ± 0.3 49.0 ± 0.1 28.4 20.1 51.5
WS_FA(20:1) 95 550 29.5 ± 0.2 36.2 ± 0.1 34.3 ± 0.2 25.8 38.1 36.1
WS_FA(20:1) 95 650 29.6 ± 0.2 41.7 ± 0.1 28.7 ± 0.2 25.9 43.9 30.2
WS_FA(20:1) 95 750 27.6 ± 0.2 43.4 ± 0.1 29.0 ± 0.2 23.8 45.7 30.5

WS:FA Ratio Experiments

WS 100 650 26.5 ± 0.2 36.8 ± 0.1 36.7 ± 0.1 26.5 36.8 36.6
WS_FA(100:1) 99 650 27.3 ± 0.2 39.8 ± 0.1 32.9 ± 0.2 26.5 40.2 33.3
WS_FA(50:1) 98 650 28.9 ± 0.2 40.5 ± 0.1 30.6 ± 0.1 22.7 44.0 33.3
WS_FA(20:1) 95 650 29.6 ± 0.2 41.7 ± 0.2 28.7 ± 0.2 25.9 43.9 30.2
WS_FA(10:1) 90 650 32.1 ± 0.2 33.1 ± 0.3 34.8 ± 0.2 24.6 36.8 38.6
FA 0 650 93.3 ± 0.1 5.0 ± 0.2 1.7 ± 0.2

°standard deviations equivalent to total product distribution.

a
by difference.

comprised of cellulose, lignin, organosolv and xylan from oat pellets
[33]. Other studies, such as micro- and nano-NiO catalyzed cellulose,
xylan and lignin pyrolysis show minimal impact on reaction kinetics
[34]. While the lack of difference in reaction rate suggests that there is
minimal or no impact of incorporating the coal fly ash into the wheat
straw, this is only one measurement on which to evaluate catalytic
activity.
3.1. Impact of pyrolysis temperature on 5 wt% fly ash in wheat straw
The yields of pyrolysis gas, bio-oil and biochar at a series of po-
tential pyrolysis temperatures (450 to 750 °C, at 100 °C increments) for
the WS/FA ratio of 20:1 were used to determine the temperature for
bulk sample pyrolysis that maximized biofuel quality and quantity
while tempering energy input (by minimizing pyrolysis temperature).
As shown in Table 2, the total solid conversion increased from 450 to
550 °C, then stayed roughly equivalent from 550 to 650 °C, and in-
creased again when heated to 750 °C. However, if we look at the second
set of product distributions in Table 2, on a per mass of biomass basis,
we find that while the biomass converted does indeed increase from
550 to 650 °C, that this increases only the gas yield, and the liquid yield
actually decreases from 550 to 650 °C. It is well documented that higher
pyrolysis temperatures generally result in lower solid char yields, and
correspondingly higher gas yields as more of the solid is devolatilized
[35,36]. Yet, yield is only one part of the pyrolysis temperature deci-
sion; a survey of the condensable and non-condensable gases reveals the
impact of temperature on specific products.
From Table 3, we see that increasing pyrolysis temperature from
450 °C to 750 °C (with a hold time of 60 min) dramatically increased the
H2 yield by over 2800%. For C2H2, C2H4, C2H6, the yields increased
significantly from 450 to 550 °C, but then saw little increase in going
from 550 to 750 °C for each gas. As temperature increases, devolatili-
zation rate increases and thermal cracking leads to the formation of
more non-condensable gases [37].
As shown in Table 4, the majority of the condensable components
identified were heterocyclic organics such as lactones (cyclic esters),
furans, phenols, and benzenediols, as well as alkenes, aldehydes, and
carboxylic acids, commonly identified for pyrolysis of lignocellulose. In
Table 4 (chromatograms available in SI) we see identified compounds
with their relative chromatogram area, normalized to pyrolyzed sample
mass and calibrated marker compounds with their concentration nor-
malized to pyrolyzed sample mass. As the pyrolysis temperature in-
creased from 450 to 650 °C, the yield of furfural, a key biorefinery in-
termediate compound, increased, and then decreased upon further
heating. At 650 °C, considerably fewer phenols and substituted ben-
zenes were detected. While the yield of phenol from biomass pyrolysis
often increases at higher temperatures, in the presence of acidic cata-
lysts phenols have been shown to alkylate [38]. Phenolic ethers are
often energetically favorable [39], though were not detected here in
appreciable quantities. Given the higher pyrolysis temperatures, and
corresponding increase in gas yields with increases in temperatures,
these compounds may well be subjected to thermal cracking, producing
CO and paraffins [40]. Others have shown that slow pyrolysis, even at
higher temperatures, tends to decrease the yields of acetic acid, phenol
(and methylated phenols), as well as other substituted aromatics [27],
as observed here.
In summation, while the total devolatilizations of the solid at 550
and 650 °C were approximately equal, there was a significant shift in
product composition, especially in the gas phase in terms of CO2 versus
H2 and CH4 yields, suggesting that the higher temperature may be
beneficial to bio-fuel production. While the yield of biochar at 650 °C
pyrolysis was only moderately higher than the yield at 750 °C (sug-
gesting slightly lower conversion at 650 °C), it is not clear that in-
creasing the temperature would be beneficial to the overall conversion.
In terms of the pyrolysis gas, the yields of C2H2, C2H4 and C2H6 were
similar at 650 °C and 750 °C. Furfural, a promising platform chemical to
produce various chemicals via oxidation, hydrogenation and con-
densation, was maximized at 650 °C, with minimal difference in 5-hy-
droxymethylfurfural (another key intermediary) yield between 650 and
750 °C. Therefore, to explore the impact of coal fly ash loading as a
catalyst for pyrolysis of wheat straw, 650 °C was selected as a pyrolysis
temperature to reduce energy input into the pyrolysis step while en-
abling a fairly complete devolatilization and conversion into desirable
platform chemicals.
3.2. Impact of fly ash on wheat straw pyrolysis products at 650 °C
As Table 2 shows, the inclusion of 1 wt% FA does not appreciably
change the overall conversion – the solid yield on a WS basis is 26.5%
for both WS and WS/FA(100:1). However, it does change the product
distribution; the 1 wt% FA shifts the product distribution to the non-
condensable gas phase. Interestingly, the specific gas component yields
vary significantly with only 1 wt% FA in the biomass; as compared to
the pure WS, the H2 yield decreases by 15%, and C2H6 by 32%, whereas
the CO2, CH4 and C2H4 yields increase. This could be due to the lower
peak temperature of pyrolysis gas components evolved versus the raw
wheat straw, evolving more CO2 as is sometimes seen for low-tem-
perature biomass pyrolysis [41]. It may also be attributed to the

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 L. Gao, J.L. Goldfarb

Table 3
Yield of pyrolysis gases ( ± 0.1 mggas/gWS) devolatilized at different temperatures and ash loadings normalized to wheat straw sample mass (WS only) and peak gas yield temperatures ( ± 1 °C; furnace K-type
thermocouple accuracy) as a function of ash loading.
Sample Wt % Pyrolysis H2 Rel CH4 Rel C2H2 Rel C2H4 Rel C2H6 Rel CO2 Rel
Biomass Temperature (°C) (mg/ change (mg/ change (mg/ change (mg/ change (mg/ change (mg/ change
gWS) (%) gWS) (%) gWS) (%) gWS) (%) gWS) (%) gWS) (%)

Pyrolysis Temperature Experiments - Pyrolysis Gas Yields

WS_FA(20:1) 95 450 0.2 8.1 0.8 9.5 0.6 54.0
WS_FA(20:1) 95 550 0.7 304% 10.9 35% 1.4 73% 12.8 36% 1.1 78% 152.2 182%
WS_FA(20:1) 95 650 2.1 1094% 15.7 94% 1.6 97% 15.7 66% 1.3 111% 167.6 210%
WS_FA(20:1) 95 750 5.2 2815% 17.8 119% 1.7 104% 14.5 54% 1.3 112% 193.9 259%

WS:FA Ratio Experiments - Pyrolysis Gas Yields

WS 100 650 2.4 13.5 1.7 12.6 1.6 143.9
WS_FA(100:1) 99 650 2.1 −15% 14.1 5% 1.5 −8% 12.7 0% 1.1 −32% 159.8 11%

100
WS_FA(50:1) 98 650 2.3 −4% 16.2 20% 1.7 2% 16.2 28% 1.4 −10% 173.1 20%
WS_FA(20:1) 95 650 2.1 −13% 15.7 16% 1.6 −1% 15.7 24% 1.3 −15% 167.6 16%
WS_FA(10:1) 90 650 2.1 −14% 14.4 7% 1.6 −5% 12.4 −2% 1.2 −22% 171.4 19%

WS:FA Ratio Experiments - Peak Pyrolysis H2 (°C) CH4 Peak 1 CH4 Peak 2 C2H2 (°C) C2H4 (°C) C2H6 (°C) CO2 (°C)
Gas Temperatures (°C) (°C)

WS 100 650 650 389 569 519 528 524 385

WS_FA(100:1) 99 650 650 383 565 519 519 520 380
WS_FA(50:1) 98 650 650 360 544 501 501 493 362
WS_FA(20:1) 95 650 633 331 517 465 474 464 329
WS_FA(10:1) 90 650 620 318 498 454 459 452 315
FA Pyrolysis at 650 °Ca H2 (mg/ H2 Peak CH4 (mg/gFA) CH4 Peak C2H2 (mg/ C2H2 Peak C2H4 (mg/ C2H4 Peak C2H6 (mg/ C2H6 Peak CO2 (mg/ CO2 Peak
gFA) (°C) (°C) gFA) (°C) gFA) (°C) gWS) (°C) gWS) (°C)
FA 0 650 1.00E-08 650 3.44E-07 206, 650 3.31E-08 – 2.43E-07 – 4.85E-08 – 104.0 202, 650
a
no peaks detected in analysis.
Journal of Analytical and Applied Pyrolysis 137 (2019) 96–105
L. Gao, J.L. Goldfarb Journal of Analytical and Applied Pyrolysis 137 (2019) 96–105

Table 4
Condensable components resulting from pyrolysis of WS/FA (20:1) at a series of different temperatures as identified via GCMS; Calibrated compounds given in
mgcompound per gWS ( ± 0.0005 mg/g).
Retention time (min) Compound 450 °C 550 °C 650 °C 750 °C
Normalized Concentration (mg/gWS)

11.6 Furfural [2-furancarboxaldehyde] 8.84E-02 2.40E-01 2.48E-01 2.01E-01

13.69 2-furanmethanol 7.91E-02 1.68E-01 8.60E-02 9.54E-02
15.79 Styrene [Ethenylbenzene] 8.02E-03 ND ND ND
17.98 2(5 H)-furanone 1.61E-02 4.03E-02 ND 8.71E-03
18.23 1,2-cyclopentanedione 1.15E-02 1.36E-02 ND 4.26E-03
21.03 5-hydroxymethyl furfural 8.21E-03 2.21E-02 5.99E-03 9.08E-03
22.43 Phenol 1.31E-02 3.28E-03 2.01E-03 3.22E-03
24.73 3-methyl-1,2-cyclopentanedione 3.48E-03 4.32E-03 ND 2.48E-03
27.73 p-cresol [4-methylphenol] 5.10E-03 1.53E-03 ND 1.16E-03
34.03 Catechol [1,2-dihydroxybenzene] 1.31E-03 ND ND 2.44E-03
40.93 Syringol [2,6-dimethoxyphenol] 1.62E-03 3.00E-03 ND 2.77E-03

Normalized Chromatogram Area (TIC/g)

7.94 Butanedial 2.01E+05 9.95E+04 4.10E+04 8.43E+04
8.35 (2 H)-furan-2-one 1.78E+04 3.67E+04 ND 1.62E+04
8.58 Butanoic acid ND 2.68E+04 1.99E+05 3.01E+04
8.77 Acetic acid ND 2.44E+05 1.10E+05 2.02E+05
9.25 2-hexene ND 3.30E+04 ND 2.21E+04
11.46 2-cyclopenten-1-one ND 4.80E+05 8.89E+05 8.22E+05
14.1 Ethylbenzene 1.00E+05 ND ND ND
17.52 Ethanone,1-(2-furanyl) 5.51E+04 1.42E+05 1.35E+05 1.47E+05
17.76 Butyrolactone 3.50E+04 1.15E+05 2.47E+04 1.97E+04
28.21 2-methoxy-phenol 9.09E+04 2.76E+04 ND 1.75E+04
28.41 Pentanal 1.52E+05 1.04E+05 4.83E+04 1.72E+05
34.27 1,4:3,6-dianhydro-,alpha,-d-glucopyranose 1.03E+04 2.64E+04 ND 2.79E+04

*
ND = not detected.

Fig. 2. Mass spectra of H2 and CH4 evolved during 650 °C pyrolysis of wheat straw and wheat straw + fly ash blends (spectra of all monitored gases available in
Supplemental Information).

mineral matter of the biomass and/or coal producing CO2 through
carbonate decomposition and/or interactions between the mineral
matter and biomass carbon, which might explain the increase in CH4
and C2H4 yields [42]. This is supported by the pyrolysis product dis-
tribution of the coal fly ash. When FA is pyrolyzed at 650 °C, the only
compound to be evolved in any appreciable quantity is CO2 (Table 3).
Thus, the higher yields of CH4 and C2H4 are not attributable to the
devolatilization of the FA alone, but must be due to an interaction
between the FA and WS. As shown in Table 3 and Fig. 2 (additional
plots available in SI), the peak temperature at which various com-
pounds were produced decreased upon incorporation of the 1 wt% FA.
These peak evolution temperatures decreased considerably as the
amount of FA included in the biomass increased, as shown in Table 3.
For many gases, including CH4, the gases were evolved at faster rates as

101
L. Gao, J.L. Goldfarb
the FA increased, suggesting that the coal fly ash may catalyze the
devolatilization of biomass samples.
For the WS/FA (10:1) sample, the inclusion of coal fly ash into the
wheat straw has a significant impact on methane devolatilized, in-
creasing the total yield (versus pure WS) by 7%, but decreasing the
peak evolution temperature by almost 70 °C. The peak temperatures of
C2H4 and C2H6 release also decrease by approximately 70 °C.
Interestingly, the peak temperature of each evolved pyrolysis gas
component shifts in a to similar lower temperatures as a function of FA
loading, with the exception of hydrogen. For example, every gas com-
ponent devolatilized at approximately 50, 20, and 5 °C lower tem-
peratures than WS for WS/FA (20:1), (50:1), and (100:1) blends, re-
spectively. As compared to the dramatic increase in gas yields seen for
different pyrolysis temperatures, the amounts of gaseous fuels were
only modestly impacted by FA loading. Overall, the hydrogen evolved
decreased for each sample including FA, from a low of 4% for the WS/
FA (50:1) blend to 13–15 % for the other blends. Likewise, C2H6 de-
creased for all samples. However, methane increased slightly upon in-
corporation of fly ash into the biomass, up to 20% for the WS/FA (50:1)
blend. Longer reaction times and higher temperatures tend to favor
recombination of smaller radicals into large gas phase molecules,
whereas lower temperatures suppress thermal cracking. The behavior
observed might be an artifact of gases evolving at lower temperatures
and shorter residence times [43]. While the fly ash appears to have a
small catalytic impact on the overall gaseous products produced –
especially at lower loadings (1 wt% data) – at higher loadings it can
significantly lower the peak evolution temperatures and, in most cases,
increase the evolution rate at which the gas is devolatilized. Given the
lack of impact of the FA on the DTG curves this was somewhat sur-
prising. One might suppose that the peak mass loss would correspond to
gaseous component evolution. However, this is not always the case; as
noted throughout the biomass pyrolysis literature, some “directly de-
volatilized” compounds (e.g. those compounds that can be direct pro-
ducts of thermal degradation such as H2O and CO2) do correspond to
peak DTG curves, but for other gaseous components, they may occur
before/after peak mass loss [44,45] as is the case here. As such, we turn
to an analysis of the condensable bio-oil via GC–MS to shed light on this
observation and to further gauge the efficacy of coal fly ash to act as a
catalyst for the pyrolysis of biomass to biofuels.
Fig. 3 compares the bio-oil components identified via GCeMS
analysis of the condensable bio-fuel trapped in methylene chloride
(DCM) during pyrolysis of the WS and WS + FA blends at 650 °C
(chromatograms and data provided in SI). Again, the primary con-
densable compounds identified were furfurals, carboxylic acids and
esters. As shown in Fig. 3, increasing the coal fly ash positively impacts
the yield of compounds with oxygen containing functional groups. That
is, compounds with eOH, eCOOH, eC]O, eCeOeC groups were
overall removed – to varying degrees and amounts – as the amount of
Fig. 3. Yield of condensable components as a function of fly ash loading for pyrolysis at 650 °C.
102
Journal of Analytical and Applied Pyrolysis 137 (2019) 96–105
fly ash in the blend increased. For example, two compounds containing
eC]O, 2(5 H)-Furanone and 1,2-Cyclopentanedione, were removed
completely when the coal fly ash to wheat straw ratio is (1:20) or
higher; interestingly the former compound peaked at the (100:1) ratio,
while the latter peaked for the pure WS, and decreased by 50% for
(100:1) blend. The concentrations of acidic compounds displayed
somewhat divergent behavior. For propanoic acid, the yield increased
with FA up to (20:1), then disappeared for the (10:1) blend; likewise,
for acetic acid the concentration peaked at (100:1) and was not de-
tected for (10:1). Conversely, butanoic acid saw a fairly similar yield for
WS, (100:1), (50:1) and (20:1) blends, but was not detected in the
(10:1) blend. The catalytic pyrolysis of biomass often proceeds via the
breaking of CeCO(OH) and CeOH bonds in decarboxylation, dec-
arbonylation and dehydration reactions [8]. It appears that the fly ash
may deoxygenate condensable liquids in terms of lowering the yield of
cyclic oxygenated groups even at low loadings, but requires more sig-
nificant quantities to reduce the acidic components. While we do not
have the ability to monitor CO production (as the reaction was run in
N2, and both show the same MS signal), the fluctuating levels of CO2
devolatilized mimic the overall results here; while there is no specific
“trend” for CO2, the additional of coal fly ash increases its yield
(overall) while decreasing (on average) the oxygenated condensable
yield.
Furfural (2-furancarboxaldehyde) is a valuable platform chemical
for the production of pharmaceuticals, resins, fungicides and other
specialty chemicals [46]. Furfural is the most common and dominant
intermediate compound during biomass pyrolysis, but its yield is
usually lower than 1 wt% [47]. Previously it was shown that the fur-
fural yield could be promoted by acid catalyzed pyrolysis processes
using catalysts such as ZnCl2, MgCl2, CaCl2, AlMCM-41, (NH)2HPO4,
Fe2(SO4)3, and Al/SBA-15 [48–58]. From Fig. 3, we see that as the
amount of coal fly ash increases from 1 wt% to 5 wt%, the furfural yield
increases by 66 then 94% (almost doubling for 5 wt% FA), then falls
back to only a 40% increase over raw wheat straw for the 10 wt% fly
ash blend. Results obtained in the present research suggest that the
weight ratio of coal fly ash to wheat straw of (20:1) is effective in both
increasing the furfural yield while decreasing some oxygenated com-
ponents. However, this is a balancing act of desirable components, as
the (100:1) blend significantly increased the 5-hydroxymethyl furfural
yield over the raw wheat straw, but at higher FA loadings the 5-HMF
yield returned to that seen without the fly ash.
Previous results showed that activated fly ash and materials ex-
tracted from fly ash are promising catalysts for various biomass reac-
tions, especially for extraction of minerals and for the production of
zeolites [59]. Here we find coal fly ash itself has a catalytic effect on
wheat straw pyrolysis. Evidence for this includes: (1) increased devo-
latilization of biomass (lower char yield) at same temperature/re-
sidence times favoring gaseous (noncondensable) products as catalyst
L. Gao, J.L. Goldfarb Journal of Analytical and Applied Pyrolysis 137 (2019) 96–105

Table 5
Characterization and application of heterogeneous WS + FA biochars prepared at 650 °C for adsorption of methylene blue from water.
Biochar Volatile matter (wt%) Fixed carbon (wt%) BET surface area (m2/g) Pore volume (cm3/g)

WS 22.73 ± 1.27 62.24 ± 0.65 5.9628 ± 0.13 0.0121 ± 0.0001

WS/FA(100:1) 17.65 ± 0.59 64.48 ± 1.67 10.397 ± 0.057 0.0189 ± 0.0001
WS/FA(50:1) 16.50 ± 1.70 65.63 ± 1.94 14.457 ± 0.132 0.0212 ± 0.0001
WS/FA(20:1) 23.38 ± 2.14 56.03 ± 2.82 21.848 ± 0.36 0.0256 ± 0.0002
WS/FA(10:1) 12.61 ± 0.68 63.02 ± 1.05 5.6655 ± 0.17 0.0119 ± 0.0001
FA 0.55 ± 0.02 18.18 ± 1.27 36.173 ± 1.33 0.0302 ± 0.0001

Langmuir isotherm Freundlich isotherm

Biochar qm(mg/g) KL(L/mg) R2 Kf [mg/g(L/mg)1/n] n R2

WS 32.4 ± 1.08 2.87E-02 ± 2.90E-03 0.985 5.60 ± 0.01 3.36 ± 0.03 0.991
WS/FA(100:1) 32.6 ± 0.19 2.10E-02 ± 1.27E-03 0.993 3.10 ± 0.03 2.46 ± 0.07 0.973
WS/FA(50:1) 44.2 ± 0.19 8.48E-03 ± 1.22E-03 0.991 1.94 ± 0.01 2.01 ± 0.02 0.999
WS/FA(20:1) 54.8 ± 0.34 5.35E-03 ± 1.32E-03 0.968 1.30 ± 0.05 1.73 ± 0.11 0.976
WS/FA(10:1) 64.7 ± 0.24 1.19E-02 ± 1.84E-03 0.934 3.01 ± 0.02 1.94 ± 0.04 0.992
FA 41.6 ± 0.05 2.99E-02 ± 4.84E-04 0.998 6.30 ± 0.02 2.97 ± 0.01 0.997

Pseudo-first-order kinetics Pseudo-second-order kinetics

Biochar K1(1/min) R2 K2(g/mg min) R2

WS 5.69E-03 ± 1.05E-04 0.961 1.63E-03 ± 2.02E-04 0.993

WS/FA(100:1) 5.83E-03 ± 2.58E-04 0.993 3.01E-03 ± 1.27E-04 0.999
WS/FA(50:1) 9.13E-03 ± 6.35E-04 0.963 3.15E-03 ± 2.23E-04 0.997
WS/FA(20:1) 4.39E-03 ± 3.52E-04 0.951 3.68E-03 ± 2.46E-04 0.996
WS/FA(10:1) 5.36E-03 ± 4.29E-04 0.946 3.73E-03 ± 2.31E-04 0.996
FA 4.96E-03 ± 5.82E-04 0.890 1.08E-02 ± 3.52E-04 1.000

loading increases up to 5 wt% with shift to condensable products at
10 wt% fly ash; (2) enhanced production of some pyrolysis gases, in-
cluding CO2, CH4, and C2H4, with significant lowering of peak gas re-
lease temperatures (up to 70 °C) as the fraction of fly ash increases; and
(3) higher yields of furfurals and lower of oxygenated compounds in the
condensable bio-oil fraction. These points suggest that the coal fly ash
could act as a catalyst in biomass pyrolysis, especially for dehydration
and deoxygenation reactions. Beyond the catalytic benefits of in-
corporating coal fly ash into biomass during pyrolysis, we explored the
potential waste-to-byproduct conversion of the heterogeneous biochars
produced for their application to water treatment.
3.3. Characterization and application of heterogeneous biochars
Biomass samples mixed with coal fly ash and pyrolyzed at 650 °C
yielded higher surface areas than the biochar alone, with the exception
of the (10:1) sample (Table 5). Interestingly, this sample had a similar
surface area and porosity to the biochar, despite the finding that the
pyrolyzed fly ash has the highest surface area of all the samples. The
porous voids that formed during devolatilization could be blocked by
the coal fly ash or may have collapsed (plausible given high volume of
gas released and small amount of volatile matter present), both of
which would lead to lower surface area and pore volume [17].
When the ratio of fly ash to wheat straw is below 1:20, both the
surface area and pore volume increase as the proportion of coal fly ash
in the blend increases; for the (20:1) sample, the increase is approxi-
mately four times higher than the biomass alone. The enhancement in
surface area and pore volume as a function of coal fly ash addition is not
an additive function of the coal fly ash’s presence. For example, if the
coal fly ash had no effect on the biochar during pyrolysis but simply was
“present” in terms of mass fraction, we might expect the resulting WS/
FA(100:1) surface area and pore volume to be 6.265 m2/g and 0.0123
cm3/g if we assume that the contribution is a weighted function of the
blends’ constituents as:
SApredict= wWSSAWS + washSAash
Where x is the mass fraction of the component in the blend (predicted
pore volume calculated analogously). In fact, the measured surface area
and pore volume were almost twice these values. This may due to the
coal fly ash promoting devolatilization and removal of the pyrolysis
products from the solid, opening pores in the material. The surface area
and pore volume of WS/FA(10:1) were almost the same as that of the
wheat straw.
Equilibrium adsorption studies on the ability of biochars to remove
methylene blue (MB) from water show maximum adsorption capacities
from 33 to 65 mgMB/gBiochar as determined via Langmuir isotherms
(Table 5). The adsorption intensity of the Freundlich isotherm, n, values
are all greater than 1. This suggests that it is thermodynamically fa-
vorable to use these heterogeneous sorbents to remove methylene blue
from aqueous solutions [60]. Given the reasonable fits of each model to
the data (with 15 data points R2 > 0.95 for every sample/model) it is
difficult to assign specific isotherm behavior based on these models.
Langmuir is often thought to describe monolayer adsorption, whereby
an equilibrium saturation point exists when the surface is saturated by
chemically adsorbed species. The Freundlich isotherm is not con-
strained by this monolayer behavior, but rather describes reversible
physisorption [61]. This ambiguity in model selection extends to the
adsorption kinetic studies.
The adsorption of MB onto all biochars appears to “follow” pseudo-
second-order kinetics as indicated by correlation coefficients
(R2 > 0.99) for all samples, a criterion often applied to deciding model
“fit.” (Table 5, Fig. S4 of the Supporting Information). However, with
an R2 > 0.94 for pseudo-first-order models and 15 data points, the as-
signment of an adsorption mechanism according to the kinetics model
using R2 values is not statistically appropriate. The inconclusive nature
of the rate law is common throughout the sorption literature for coal fly
ash and fly ash + biomass sorbents [62]. We suspect that this is because
the adsorption is both dependent on bulk MB concentration and capa-
city (first-order) and on chemisorption involving valency forces be-
tween sorbent and sorbate (second-order). Given the heterogeneity of
the biomass and, more importantly, the coal fly ash (as described in
(5) Table 1), the potential for sorption to be governed by both diffusion and

103
L. Gao, J.L. Goldfarb
surface complexation – and, as noted above, by both physical and
chemical forces – is not surprising. Such concerted adsorption forces
have been observed throughout the literature [62].
Prior research suggests that high surface area and pore volume are
linked to greater adsorption of pollutants onto solid adsorbents [20,63],
however these are not directly correlated, as recent research shows
[64]. The WS/FA(10:1) sample, with moderately lower surface area and
pore volume than other biochars used in this study, shows moderately
higher adsorption capacities than the other samples, as seen in Table 5
(and Fig. S5 of Supplemental Information). The WS/FA (20:1) and
(10:1) samples have a faster rate of adsorption compared with the other
biochars, especially the raw WS. The WS/FA(10:1) sample, with a
surface area and pore volume of 5.66 m2/g and 0.0119 cm3/g, had the
highest adsorption capacity and fastest adsorption kinetic rate for the
methylene blue, of 64.715 mg/g and 3.73E-3 g/(mg·min), as compared
to the almost same surface area and pore volume of pure WS with an
adsorption capacity and rate constant of 32.398 mg/g and 1.63E-3 g/
(mg·min). Sample WS/FA(20:1), with a surface area and pore volume of
21.848 m2/g and 0.0256 cm3/g, had a moderate lower capacity and
rate (54.839 mg/g and 3.68E-3 g/(mg·min) than WS/FA(10:1).
The addition of the coal fly ash to the biomass also shows synergistic
effects (rather than additive) in terms of adsorption capacities. Just as
the relationship between surface area and fraction of coal fly ash pre-
sent in the mixture was not additive (per Eq. (5)), neither is the ad-
sorption capacity. The pyrolyzed fly ash had a higher adsorption ca-
pacity than the biochar pyrolyzed at the same conditions, and for the
(100:1) sample the fly ash had no measurable impact on the adsorption
capacity (or rate). However, again we see that as the proportion of fly
ash increases, the adsorption capacity increases – but this time con-
siderably higher than might be predicted by an additive relationship.
Using Eq. (5), we would expect the adsorption capacity of all the fly ash
containing mixtures to be around 32–33 mg/g. However, the adsorption
capacities were clearly much higher. This suggests, just as observed for
the surface area enhancements, bio-oil quality enhancements, and
pyrolysis gas yield increases that the fly ash acts as a catalytic material
to increase devolatilization and improve the porous nature of the re-
sulting heterogeneous adsorbents.
4. Conclusions
Solid waste disposal – be it coal fly ash or residual biomasses –
strains the environment in many ways, and may well be mitigated
through the conversion of waste to renewable energy and sustainable
materials for water treatment. The present study demonstrates the
possibility of using fly ash from the combustion of a bituminous coal to
in situ catalyze the pyrolysis of wheat straw, an abundant agricultural
biomass. The inclusion of coal fly ash did not significantly impact the
overall reaction rate, but it did lower the temperature at which many
noncondensable gaseous species were released (potentially lowering
the energy required to pyrolyze more of the biomass), and resulted in a
condensable liquid with fewer detectable oxygenated components and
an increase in furan, a key biorefinery intermediary. As the weight
fraction of fly ash in the biomass increased from 1 to 10 wt%, the
overall conversion of solid biomass increased; 1–5 wt% fly ash favored
conversion to the gas phase (especially CO2, CH4 and C2H4), whereas
the 10 wt% mixture produced more condensable species. For a more
complete waste-to-byproduct transformation, we probed the ability of
the resulting heterogeneous wheat straw-fly ash biochars to removed
methylene blue from water as a simulated organic pollutant. Like many
heterogeneous biomass-mineral systems, there is ambiguity in de-
termining whether or not the adsorption is physically or chemically
motivated; likely it is a combination of mechanisms given the hetero-
geneity of the mineral matter comprising both the biomass and coal fly
ash. However, the incorporation of the fly ash significantly improves
the surface area and adsorption capacity of the heterogeneous biochars,
above what might be predicted from an additive relationship,
104
Journal of Analytical and Applied Pyrolysis 137 (2019) 96–105
suggesting synergistic, catalytic behavior of the coal fly ash in pro-
moting devolatilization. Overall, we find that coal fly ash may be a
potential inexpensive catalyst for in situ upgrading of biomass pyrolysis,
producing heterogeneous sorbents with enhanced adsorption capacities
for organic pollutants.
Acknowledgements
L. Gao acknowledges the support of the Fundamental Research
Funds for the Central Universities (No. 2017BSCXA15), the
Postgraduate Research & Practice Innovation Program of Jiangsu
Province (No. KYCX17_1515) and the China Scholarship Council. The
authors appreciate the assistant of Quantachrome with surface area
analysis of the fly ash. The authors sincerely thank the anonymous
Reviewers who significantly improved this manuscript.
Appendix A. Supplementary data
Supplementary material related to this article can be found, in the
online version, at doi:https://doi.org/10.1016/j.jaap.2018.11.014.
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