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Effects of Dilute Phosphoric Acid Treatment on Structure and Burning

Characteristics of Lignocellulosic Biomass

Article in Journal of Energy Resources Technology, Transactions of the ASME · February 2019
DOI: 10.1115/1.4042719

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H. Haykiri-Acma
Istanbul Technical University,
Chemical and Metallurgical Engineering Faculty,
Chemical Engineering Department,
Maslak, Istanbul 34469, Turkey
S. Yaman1
Istanbul Technical University,
Chemical and Metallurgical Engineering Faculty,
Chemical Engineering Department,
Maslak, Istanbul 34469, Turkey
e-mail: yamans@itu.edu.tr
Effects of Dilute Phosphoric Acid
Treatment on Structure and
Burning Characteristics of
Lignocellulosic Biomass
Pretreatment of biomass with phosphoric acid (H3PO4) has been a popular method since
it facilitates the generation of biofuels and mitigates the problems arising from the use of
corrosive sulfuric acid that is otherwise commonly employed for pretreatment. However,
variations took place in the structure of biomass through this treatment have not so far
been investigated in detail. This paper focuses on the effects of aqueous H3PO4 treatment
on the lignocellulosic residue of corn (CR) considering the fuel properties, ash fusion
temperatures, combustion characteristics and kinetics, mineral phases, surface function-
alities, and the morphology of the treated biomass. It was determined that interaction of
biomass with 5% H3PO4 solution led to important variations from cellulose crystallinity
to thermal reactivity of this lignocellulosic material. Although elements such as Na, K,
Ca, Mg, and Fe could be effectively removed by treatment, formation of phosphorus con-
taining new phases caused to increase in ash yield. Also, the change in mineral matter
composition led to an increase in ash fusion temperatures along with reduction in the
burning rates. Thus, the combustibility and combustion performance indices dropped.
[DOI: 10.1115/1.4042719]

Keywords: phosphoric acid, biomass, corn residue, ash fusion, burning

1 Introduction inhibit the fermentation process. The pretreatment of biomass

with phosphoric acid (H3PO4) is able to mitigate the problems
First-generation biofuels that have been produced using sugar
seen with H2SO4. H3PO4 that is less aggressive than commonly
and vegetable oil accompany ethical problems due to competition
used acids in hydrolysis of biomass is more expensive than
between the food- and fuel-sectors over the edible sources, and
H2SO4. However, it is reported that the use of H3PO4 provides
lead to an increase in the prices of crops. In contrast to this,
coproducts that may be used as plant fertilizers along with the
second-generation biofuels that are produced from inedible ligno-
other advantages such as showing lower level of toxin production
cellulosic biomass avoid using inadequate food sources in fuel
and corrosivity [6,7]. The use of H3PO4 also has a lower environ-
sector. Agricultural residues, forest products, and dedicated crops
mental impact since most of the value-added chemicals (phos-
are some of the well-known lignocellulosic biomass species.
phate, N, K, Mg, and trace metal) can be recovered and used as
Although lignocellulosic biomass has great global potential,
fertilizer [8]. whereas the use of dilute H2SO4 causes concerns
biofuel generation from which requires expensive and time-
associated with sulfur contamination in the products. H3PO4 at
consuming pretreatment to remove the cellulose crystallinity and
low concentration presents a high capacity of solubilizing the
to change the biomass structure to a new form that is easily acces-
hemicellulose fraction of biomass with the advantage of being a
sible by reagents in subsequent steps [1,2]. That is, the lignin in
source of phosphorous, a nutrient for the microorganism in the
biomass serves as a protective shield to the external effects; hence,
subsequent fermentation [8]. Besides, the use of the H3PO4 at
the accessibility of the chemicals/enzymes needs an effective pre-
moderate temperatures (around 50  C) makes the biomass amor-
treatment that alters the biomass structure. Pretreatment of ligno-
phous by disrupting hydrogen bonds that facilitates the sequential
cellulosic biomass is particularly necessary to increase the yields
stages like enzymatic digestion by enlarging the surface area [9].
of sugars for downstream fermentation [3]. There have been vari-
The effect of the dilute H3PO4 pretreatment on the functional
ous pretreatment approaches including mechanical comminution,
groups of the wheat bran cellulose was determined with 78%
steam explosion, ammonia fiber explosion, CO2 explosion, ozon-
reduction in the cellulose crystallinity index [10]. Treatment of
olysis, acid hydrolysis, alkaline hydrolysis, organosolv, pyrolysis,
biomass with H3PO4 also results in formation of phosphorus-rich
pulsed electrical field, biological, etc. [4,5]. Of which, the method
carbons through the combination of organic species with acid to
of acid hydrolysis is of great interest due to being an easy, cheap,
form phosphate and polyphosphate bridges that connect and cross-
and rapid procedure. The dilute acid hydrolysis method is usually
link polymer fragments [11]. Phosphorus acts as an important
performed using acid concentrations of 2–5% under various tem-
inhibitor for oxidation that is the most desirable characteristics of
perature and pressure conditions. The acid of choice in most cases
strong carbon composites and durable catalysts [11]. It is also
has been sulfuric acid (H2SO4) that brings unavoidably problems
known that H3PO4 is added as a fire retardant for wood and cellu-
such as being highly corrosive and formation of chemicals that
lose materials [12].
Treatment/impregnation of biomass with H3PO4 has been
1
Corresponding author. attempted for various purposes such as the chemical activation of
Contributed by the Advanced Energy Systems Division of ASME for publication activated carbon [11,13–17], xylose production from pinewood saw-
in the JOURNAL OF ENERGY RESOURCES TECHNOLOGY. Manuscript received October 2,
2018; final manuscript received January 28, 2019; published online February 14, dust through hydrolysis [6], bioethanol production from eucalyptus
2019. Assoc. Editor: Ashwani K. Gupta. by H3PO4 impregnation [3], production of anhydro-saccharides by

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 fast pyrolysis [18], thermal degradation of seaweed [19], prepara-
tion of supercapacitor electrodes from apricot stones and peach
stones [20], production of gasoline-grade biofuel from renewable
polyhydroxybutyrate [21], fermentable sugar production from
rapeseed straw [8], alternative solvent for cellulose since concen-
trated H3PO4 (beyond 83%) dissolves cellulose [9], ethanol pro-
duction from wheat bran [10], preparation of oxidation resistant
activated carbons [11], changing the pyrolysis characteristics of
apple pulp [16], production of pyrolytic gases [12], etc. On the
other hand, the impregnation way of biomass with H3PO4 differs
in literature. Castro et al. [3] soaked eucalyptus chips at room tem-
perature for 4 h in dilute acid solutions at concentrations of
0.5–1% w/w to impregnate the biomass from the dilute solutions.
Dobele et al. [18] impregnated biomass with H3PO4 by heating
the samples at 100  C for 1 h in aqueous acid solutions of
0.05–3.0%. Hu et al. [19] washed seaweed with H3PO4 solution of
7%. Lopez-Linares et al. [8] mixed rapeseed straw and H3PO4
solution at a liquid–solid ratio of 12% (w/v). Nair et al. [10] pre-
treated wheat bran with dilute H3PO4 at concentrations of
0.5–3.0% w/v at temperatures of 150–210  C for interaction times
of 5–20 min.
The most of the studies in literature where H3PO4 was
employed to biomass usually focuses on the effectiveness of this
treatment on the yields of subsequent stages. Accordingly, these
studies are usually related to improving either the enzymatic
hydrolysis efficiency to produce bioethanol or the chemical acti-
vation of activated carbon. Alternatively, this paper rather deals
with what happens on the structure and properties of biomass
when H3PO4 is used. In this context, the lignocellulosic residues
of corn was treated with dilute H3PO4 solution, and the effects of
this interaction on the fuel properties, cellulose crystallinity, com-
bustion behavior, ash fusion temperatures, etc. were investigated.
Also, the lignocellulosic residues left in corn field offer great
energy potential, and this renewable and sustainable energy
source may be evaluated as an alternative fuel or feedstock
through characterization of its fuel properties in detail.
2 Materials and Methods
The herbaceous lignocellulosic residue of corn (CR) used in
this study was Turkish origin. The residue was first kept in labora-
tory in an open tray, and then dried in oven at 60  C. The dried
sample was milled and sieved to get the particles less than 2 mm.
The proximate analysis was performed according to ASTM stand-
ards, and the higher heating value (HHV) was determined by IKA
C2000 model calorimeter. The ultimate analysis was carried out
R
using Leco TruSpecV CHN model with S module elemental
analyzer. Macromolecular ingredients (cellulose, hemicellulose,
lignin, and extractives) were determined via wet analysis
methods, for which CR was first treated with benzene/ethyl alco-
hol solutions to determine the content of extractives according to
the ASTM D1105 method, and then the extracted bulk was treated
again according to Wise’s chlorite procedure [22] and van Soest
method [23] to estimate the holocellulose (cellulose þ hemicellulose)
and lignin contents, respectively.
X-ray diffraction (XRD) examination was performed in the
range of 10 deg < 2h < 90 deg using Bruker Axs D8 ADVANCE
model X-ray diffractometer. Scanning electron microscopy
(SEM) images were obtained using Quanta 250 FEG device, while
Fourier transform infrared (FTIR) spectra were obtained using
Perkin Elmer FTIR Spectrum 100 Spectrometer.
The pretreatment of biomass was performed using 5 vol %
aqueous solution of H3PO4. In the literature, interaction of various
biomass species with H3PO4 has usually been conducted using
H3PO4 solutions that have concentrations either in the range of
0.5–5% for pretreatment or higher than 83% to dissolve the cellu-
lose ingredient. For this reason, we decided to employ 5 vol %
aqueous solution of H3PO4 to limit the effects of interaction only
with pretreatment that dissolves hemicellulose, extractable
unsteady constituents, and some of minerals. Pretreatment of the
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sample was simply performed by keeping the biomass in solution
for 2 h and then filtering the leached bulk through a Gooch cruci-
ble (4P). The leached sample was dried in an oven for one day,
and the sequential analyses and experiments were performed on
this dried material. Likewise, distilled water and 5 vol % aqueous
solutions of HCl, H2SO4, HNO3, NaOH, and CH3COOH were
also used to pretreat biomass to compare the influence of H3PO4
solution on demineralization. The elements of interest are K, Na,
Mg, Ca, and Fe in biomass that contribute to ash/deposit forma-
tion, and hence the concentrations of these elements before and
after treatment were compared.
Ashing of the sample was performed using Heraeus D-6450
Hanau M110 model furnace through stepwise heating at 200  C
for 1 h and then at 400  C for another 1 h, followed by keeping at
600  C where it stood for 2 h to get the ash. The ash fusion runs
were carried out using ENDA ET furnace that has proportional-
integral-derivative (PID) temperature controller. For which, ten
grams of ash was melted to determine the temperatures of first
deformation (FDT), softening (ST), melting (MT), and flowing
(FT).
The dissolution of the ashes was carried out by leaching 1 g of
ash with 50 mL of Aqua Regia that contains the mixture of 30 mL
of HCl, 10 mL of HNO3, and 10 mL of distilled water. The acidic
mixture that is a yellow fuming corrosive mixture of nitric acid
and hydrochloric acid has long been used to dissolve metals and
inorganics. The treated ash was filtered through blue-ribbon filter
paper placed in a funnel, and the obtained liquid phase was ana-
lyzed using inductively coupled plasma technique that employs
Perkin Elmer Optima 2100 DV Optic emission spectrometer to
detect the concentrations of Na, K, Ca, Mg, and Fe.
Burning profiles were performed using TA Instruments
SDTQ600 model thermal analyzer, which has 0.1 lg balance sen-
sitivity, temperature range of up to 1500  C, platinum/platinum-
rhodium thermocouples, temperature sensitivity of 0.001  C, and
alumina reference material. For this, around 10 mg of sample was
heated from ambient to 900  C with a heating rate of 40  C/min
under dry air flow of 100 mL/min and allowed to stand at this tem-
perature until the weight loss completed. Borchardt & Daniels
(B&D) kinetic analysis method that is based on the differential
scanning calorimetry curve was used to determine the reaction
order (n), activation energy (EA), pre-exponential factor (A), and
the heat of reaction (DH). The ignition index [Ci, %/min3]
[24–26], the burnout index [Cb, %/min4], the comprehensive
combustibility index [S, %2/( C3 min2)] [24–26], and the burning
stability index [DW, %/(min K2)] [27] were calculated according
to Eqs. (1)–(4) to evaluate the combustion performance of the
sample
 
dw
dt max
Ci ¼ (1)
ðti  tmax Þ
 
dw
dt max
Cb ¼   (2)
Dt12  tmax  tb
   
dw dw
dt max dt mean
S¼ (3)
ðTi 2  Tb Þ
 
dw
dt max
DW ¼ (4)
ðTi  Tb Þ
where (dw/dt)max is the maximum rate of mass loss (%/min);
(dw/dt)mean is the mean rate of mass loss (%/min); ti: ignition
time (min); tmax: peak time (min); Dt1/2 is the time zone of
Transactions of the ASME
 Fig. 1 Experimental procedure

(dw/dt)/(dw/dt)max ¼ 1/2, (min); tb: burnout time (min), Ti is the The volatile matter (VM) to fixed carbon (FC) ratio is 5.32 that
ignition temperature ( C); Tb is the burnout temperature ( C). indicates this sample is a typical lignocellulosic waste material,
Schematic of the experimental procedure is given in Fig. 1. burning quickly because of the high thermal reactivity due to high
All of the experiments were repeated at least three times, and oxygen content [1,28]. Besides, the ash yield of CR is bigger than
data that deviate more than 65% than the average were not those of the woody biomass species, and it is comparable with
considered. those of the waste biomasses which are rich in inorganics. Never-
theless, HHV of CR is a bit higher or at least comparable with
3 Results and Discussion those of the brown coals. Besides, holocellulose that is the sum of
cellulosics and hemicellulosics accounts for 58.3% of the sample,
3.1 Sample Characterization. Analysis results of the raw and 14.6% of which is comprised of a-cellulose. Meanwhile, this
CR are given in Table 1. biomass is highly rich in extractives that include extractable
waxes, salts, fats, nonstructural sugars, proteins, phytosterols, and
some mineral matter. The ash fusion temperatures of this biomass
Table 1 Analysis results of raw CR and treated sample indicate that the difference between the temperatures of FDT and
FT is 113  C that is relatively a narrow range in which the ash
Raw Treated
starts to deform, softens, melts, and flows. On the other, potassium
Proximate analysis (%, ad) Moisture 6.1 7.2
is by far the most dominant element in ash followed by calcium
VM 72.9 59.1 that show catalytic activity during thermal conversion processes
FC 13.7 20.4 [29,30].
Ash 7.3 13.3
Ultimate analysis (%, daf) C 36.5 n/a
H 8.4 n/a 3.2 Effects of Phosphoric Acid Treatment
N 1.2 n/a 3.2.1 Effects on the Biomass Structure. Comparison of the
S — n/a
proximate analysis, HHV, main elements in ash, and the ash
O 53.9 n/a
fusion temperature results of the raw biomass and the biomass
HHV (MJ/kg, ad) HHV 15.5 14.2 treated using H3PO4 solution is shown in Table 1.
Macromolecules (%, ad) Holocellulose 58.3 n/a Treatment by H3PO4 solution led to an increase in the FC con-
a-cellulose 14.6 n/a tent of biomass at the expense of the VM content. Meanwhile, the
Lignin 12.6 n/a ash yield increased significantly because of the formation of phos-
Extractives 20.6 n/a
phorus containing new mineral phases [11] that will be explained
Elements in ash (%) Na 0.82 0.18 in subsequent parts of the paper. Kazmierczak-Razna et al. [14]
K 49.83 23.40 also reported such an increase in the ash yield of low quality hay
Ca 14.85 8.40
upon treatment by H3PO4. Ash fusion temperatures were also
Mg 4.74 0.82
Fe 0.15 0.02 affected from the applied treatment. Although FDT was not
almost differed, the temperatures of ST, MT, and FT shifted to
Ash fusion temperatures ( C) FDT 978 980
elevated temperatures. The increases created in temperatures of
ST 993 1049
MT 999 1089 ST, MT, and FT showed regular trend and reached 56, 90, and
FT 1091 1228 137  C, respectively. The increase in the ash fusion temperatures
is of technological importance because the fuels that have rela-
Note: ad—air-dried basis, daf—dry-ash-free basis, HHV—Higher heating tively low fusion temperatures tend to form sticky deposits on the
value, FDT—First deformation temp., ST—Softening temp., MT— inner surfaces of the burning systems that causes costly mainte-
Melting temp., FT—Flowing temp. nance need and lowers the overall efficiency.

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 Fig. 2
Figure 2 shows the XRD spectra of the raw and treated CR. The
dominant phases in the raw CR are organic C4Cl4N2, and some
potassium-containing phases such as C4H3KO8.2H2O, KCl, and
K2ClO3N. This shows that potassium compounds account for the
most significant inorganics in raw CR, and it is convenient with
the high content of potassium in ash shown in Table 1. Also, chlo-
rine is available in both organic and inorganic parts. Treatment of
CR with H3PO4 made carbon as one of the strongest phases.
In addition, some other organic phases such as C3H3N7O2,
C4H7NO4, and C2H11N2O4P that contain neither Cl nor K were
determined. Consequently, the efficient removal of K is also con-
firmed from these XRD spectra. Meanwhile, phosphorus coming
from H3PO4 introduced to the structure, and this explains the
increasing ash yield upon treatment. In this context, Rosas et al.
[11] reported that residual phosphorus is mostly in C-O-PO3 and
C-PO3 groups.
In addition, the change in cellulose crystallinity can also be
estimated from the XRD intensities. I002 is the intensity of crystal-
line region at 2h ¼ 22.5 deg, while Iam is the intensity of the amor-
phous region at 2h ¼ 18.7 deg [31]. Thus, the crystallinity index is
calculated as follows:
 
I002  Iam
crystallinity index ¼  100 (5)
I002
The intensities at 2h ¼ 22.5 deg and 2h ¼ 18.7 deg are 88 and 66
for raw CR and 116 and 109 for treated CR, respectively. Hence,
the crystallinity index was calculated 0.25 for raw CR, while it
was only 0.06 when treatment was applied. This reduction corre-
sponds to 76% decrease in the cellulose crystallinity, and it is
highly comparable with the result in literature reported by Nair
et al. [10] who found 78% reduction in cellulose crystallinity for
bran cellulose. This indicates that the crystallinity of cellulose
was mostly removed, and 5% H3PO4 solution is able to change
the organic part of lignocellulose in the favor of amorphous struc-
ture that makes it easier to process compared to biomass with high
cellulose crystallinity.
Figure 3 shows the FTIR spectra of the raw and treated CR.
Lignin is known as the only aromatic constituent in lignocellulo-
sic biomass, and the FTIR band at 1570 cm1 of raw CR can be
attributed to the aromatic C ¼ C bands of lignin. Similarly, aro-
matic skeletal C ¼ C vibration formed the band at around
1400 cm1. Meanwhile, NO2 bending in aromatic nitro groups
formed the band at 892 cm1, while the band at 1032 cm1 is
resulted from C-O-C vibrations of ether like substances. Besides,
the bands around 2911 cm1 and 3274 cm1 can be attributed to
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XRD spectra
CH3 in aromatic ring and O-H stretching, respectively. The main
difference in the FTIR spectrum taken place as a result of the
treatment is that N-H in-plane bending became an apparent band
at 1635 cm1. Also, the bands of the C-O-C vibrations of ether
like substances shifted to 982 cm1 from 1032 cm1. Huang et al.
[20] impregnated rigorously fruit stones with phosphorus keeping
the weight ratio of H3PO4/fruit stone as 0.89 and proposed that
H3PO4 acts as an effective oxidant to form C-O bonds. However,
since H3PO4 solution in our experiment was not as concentrated
as the mentioned study, the increase in the intensity of C-O bands
was not so evident. The intensity of O-H bands showed a bit
decrease, and this was also reported by Hu et al. [19] who treated
seaweed with 7% H3PO4. They proposed that hydrolysis reaction
or carbohydrates dehydration reaction might be responsible for
the reduction in the intensity of O-H bands.
SEM micrographs of the raw and treated CR are shown in
Fig. 4. The inorganic-rich nature of CR led to high reflectance in
these micrographs. The raw CR has amorphous structure with
layers stacked on another. The SEM image of the treated CR
revealed that the treatment led to the formation of a more porous
structure due to reduction in volatiles and extractable ingredients
such as extractive matter and some inorganics. This is convenient
with the literature [11,19].
3.2.2 Effects on the Burning Properties. Figure 5 illustrates
the burning profiles of the raw and treated CR. The weight loss
characteristics showed that the raw CR completed its weight loss
at around 450  C, while the weight losses went on until the final
temperature (900  C) when the sample was treated with H3PO4.
Rosas et al. [11] also reported a similar behavior that the H3PO4-
impregnated lignocellulosic materials were highly stable under
oxidizing conditions. Besides, it is also seen that the raw sample
lost most of its weight whereas a great portion of the initial weight
remained when CR is treated. Derivative thermogravimetry
(DTG) curves indicate the significant difference in the thermal
reactivities of the samples. Although the ignition point (Ti) low-
ered from 306  C to 217  C, the treatment of the CR with H3PO4
leads to important reduction in the burning reactivity. That is, the
maximum burning rate (dw/dt)max and its temperature (Tmax) are
140.2%/min and 309  C, and 22.4%/min and 274  C for raw and
treated samples, respectively. Treatment with acids may destroy
some covalent bond structure that lowers the maximum burning
rate and the corresponding temperature [19]. For this reason, the
range of burning temperatures broadened due to a decrease in the
burning rates, and a similar behavior was also reported by Hu
et al. [19]. The serious reduction in the (dw/dt)max may be
Transactions of the ASME
 Fig. 3 FTIR spectra

Fig. 4 SEM micrographs (31000)

attributed to leaching of hemicellulose that contributes to the ther-
mal reactivity. In addition, the elements that show catalytic activ-
ity can be extracted by treatment that makes the burning of the
sample slower. On the other hand, the two individual peaks seen
on the differential scanning calorimetry and differential thermal
analysis (DTA) curves resulted from the burning of the volatiles
mainly from polysaccharides (hemicellulose and cellulose) and
fixed carbon, respectively [32]. However, treatment changed this
burning regime and led to a combined region of heat flows or tem-
perature differences. Some data revealed from the burning profiles
are given in Table 2.
Data given in Table 2 were used to calculate the combustion
performance indices, and the results of these calculations are
shown in Table 3. Treatment with H3PO4 caused significant drops
in the combustion performance indices such as the ignition index
(Ci), the burnout index (Cb), the combustibility index (S), and the
burning stability index (Dw). Although the ignition point reduced,
this reduction was compensated by the decrease in (dw/dt)max.
The reduction in the extent of (dw/dt)max made the combustion
performance indices lower, since this parameter is in the numera-
tor of all the equations used to calculate these indices. This finding
is convenient with the fire retardant behavior of the phosphorus
containing materials. Comparison of the kinetic parameters is also
given in Table 3. The order of reaction (n), activation energy (EA),
and the pre-exponential factor (logA) decreased, while some
increase was detected in heat of reaction (DH).

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 Fig. 5 Burning profiles

Table 2 Summary of burning characteristics

Sample Ti ( C) Tmax ( C) Tb ( C) (dw/dt)max (%/min) (dw/dt)mean (%/min) ti (min) tmax (min) tb (min) Dt1/2 (min)

Raw 306 309 482 140.2 5.92 7.29 7.31 11.79 7.19
Treated 217 274 800 22.4 3.53 5.37 6.76 19.90 6.36

Ti is the ignition point, Tmax is the peak temp., Tb is the burnout temp., (dw/dt)max is the maximum rate of mass loss, (dw/dt)mean is the mean rate of mass
loss, ti is the ignition time, tmax is the peak time, tb is the burnout time, and Dt1/2 is the time zone of (dw/dt)/(dw/dt)max ¼ 1/2.

3.2.3 Effects on the Inorganics and Ash Fusion. The effects Table 4 shows the results of this comparison, and the HHVs after
of H3PO4 on the removal of ash-forming elements including Na, these treatments were also included to this table to better justify
K, Ca, Mg, and Fe were compared with those of H2O and 5 vol % the effects of the solutions. H3PO4 resulted in the highest removal
aqueous solutions of HCl, H2SO4, HNO3, NaOH, and CH3COOH. rates in all of the elements of interest. However, in literature the
effectiveness of H3PO4 toward demineralization was reported to
lay between H2SO4 and HCl (the less effective one) when the con-
Table 3 Combustion performance indices and kinetic parameters centrations of the acids are 7% [19]. On the other hand, the pros
and cons of these solutions should be justified taking the HHV
Raw Treated recovery after leaching into account. In terms of HHV recovery,
Combustion performance indices
Ci (%/min3) 14.8  104 3.77  104
Table 4 Effect of solution type on ash composition and HHV
Cb (%/min4) 0.226 0.026
S (%2/( C3 min2)) 18.4  106 2.1  106
Ash composition (%)
DW (%/(min K2)) 9.5  104 1.3  104
Kinetic parameters Solution Na K Ca Mg Fe HHV (MJ/kg)
n 3.79 2.06
EA (MJ/kg) 186.2 36.2 — (raw) 0.82 49.83 14.85 4.74 0.15 15.5
logA (1/min) 15.8 1.85 H3PO4 0.18 23.39 8.40 0.82 0.02 14.2
DH (kJ/kg) 4599 6574 H2O 0.81 46.18 13.42 4.59 0.13 17.3
Standard error (1/s) 0.15 0.22 HCl 0.75 49.42 10.27 3.95 0.10 16.8
H2SO4 0.34 40.34 9.99 4.45 0.07 10.9
Note: Ci, ignition index (%/min3); Cb, burnout index (%/min4); S, com- HNO3 0.51 45.37 9.58 3.58 0.13 15.1
bustibility index (%2/( C3 min2)); Dw, burning stability index (%/(min CH3COOH 0.31 48.21 11.12 3.92 0.12 17.0
K2)); n, Order of reaction; EA, activation energy; A, Pre-exponential factor; NaOH 49.93 19.39 9.13 0.56 0.01 9.7
DH, heat of reaction.

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 the solutions can be ranked in the decreasing order of References
H2O > CH3COOH > HCl > HNO3 > H3PO4 > H2SO4 > NaOH.
The chemicals such as NaOH and H2SO4 caused serious decom- [1] Klass, D. L., 1998, Biomass for Renewable Energy, Fuels, and Chemicals,
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[30] Yan, Y. F., Feng, S., Zhang, L., Li, L., Zhang, L., and Yang, Z., 2018,
“Experimental Research on Catalytic Combustion Characteristics of Inferior
Coal and Sludge Mixture,” ASME J. Energy Resour. Technol., 140(3),
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Enriched Combustion of Low-Quality Fuels at Low Temperatures,” ASME J.
Energy Resour. Technol., 141(1), p. 012101.
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