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Conversion of biomass residual to acid-modified bio-chars for efficient

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ISSN: 0306-7319 (Print) 1029-0397 (Online) Journal homepage: https://www.tandfonline.com/loi/geac20

Conversion of biomass residual to acid-modified

bio-chars for efficient adsorption of organic
pollutants from industrial phosphoric acid: an
experimental, kinetic and thermodynamic study

Mohamed H. Taha, Samir A. Abdel Maksoud, Mohsen M. Ali, Ahmed M. A. El

Naggar, Asmaa S. Morshedy & Amir A. Elzoghby

To cite this article: Mohamed H. Taha, Samir A. Abdel Maksoud, Mohsen M. Ali, Ahmed M. A. El
Naggar, Asmaa S. Morshedy & Amir A. Elzoghby (2019) Conversion of biomass residual to acid-
modified bio-chars for efficient adsorption of organic pollutants from industrial phosphoric acid: an
experimental, kinetic and thermodynamic study, International Journal of Environmental Analytical
Chemistry, 99:12, 1211-1234, DOI: 10.1080/03067319.2019.1618459

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INTERNATIONAL JOURNAL OF ENVIRONMENTAL ANALYTICAL CHEMISTRY
2019, VOL. 99, NO. 12, 1211–1234
https://doi.org/10.1080/03067319.2019.1618459

ARTICLE

Conversion of biomass residual to acid-modified bio-chars

for efficient adsorption of organic pollutants from industrial
phosphoric acid: an experimental, kinetic and
thermodynamic study
Mohamed H. Tahaa, Samir A. Abdel Maksoudb, Mohsen M. Alia,
Ahmed M. A. El Naggarc, Asmaa S. Morshedyc and Amir A. Elzoghbya
a
Nuclear Materials Authority, P.O. Box 530, El Maddi, Cairo, Egypt; bChemistry Department, Faculty of
Science, Port Said University, Port Said, Egypt; cEgyptian Petroleum Research Institute (EPRI), 1 Ahmed El-
Zomor St., Nasr City, Cairo, Egypt

ABSTRACT ARTICLE HISTORY

This study reports the removal of organic matters from phosphoric Received 8 February 2019
acid using waste-produced bio-charcoal structures. Particularly, the Accepted 16 April 2019
freshly made bio-char species via pyrolysis and two sub-driven acids KEYWORDS
activated charcoals were applied during the removal process. The Organic matters; adsorption;
treated charcoal with hydrochloric and nitric acids had attained a phosphoric acid purification;
higher adsorption rate for organic matters than that of the non- activated charcoal;
treated one. Removal percentages of 70% and 60% were, respec- separation processes
tively, attained by acid-modified chars. The kinetics of the adsorption
process was fitted via pseudo-first/second-order and Morris–Weber
models. The thermodynamic parameters of the presented sorption
process indicate that organic matter removal has been endothermic,
physical and spontaneous.

1. Introduction
Natural organic matter (NOM) is a combination of anionic molecules with carboxylic and
phenolic surface functional groups, which are mainly produced from the decomposition
of animal residues and plants [1]. In other words, NOM is a mixture of organic materials
including fulvic acid, humic acid (HA), hydrophilic acid, protein, lipid, hydrocarbons and
amino acids. Humic substances (mainly humic and fulvic acids) are the main compounds
of NOM [2,3].
Organic compounds are naturally present in phosphate rocks coming from biological
sediments of sea organisms [4]. The organics are introduced into the phosphoric acid as
impurities from the phosphate ore during the phosphoric acid production using the wet
process. There are a few studies interested by the identification of OM present in
industrial phosphoric acid. Such organic compounds consist essentially of di-n-butyl
phthalate (C16H22O4), aromatics, humic compounds, fulvic acid and other oxidised
hydrocarbons, which are mostly saturated and unsaturated fatty acids from C8, to C30,
in addition to palmitic and oleic acids and some insoluble matters [5–8].

CONTACT Mohamed H. Taha dr.mohamedp@gmail.com

© 2019 Informa UK Limited, trading as Taylor & Francis Group
1212 M. H. TAHA ET AL.

These organic compounds result in foam stabilisation in the digestion tank and above
the filters, affect crystallisation of gypsum and give dark coloured acids [9]. Accordingly,
the presence of these organic compounds affects the quantity and quality of the
produced phosphoric acid [10]. In addition, the presence of organic matter (OM) in
phosphoric acid is considered as a source of operating problems in the purification of
phosphoric acid using solvent extraction technique. Same difficulty is faced in the
uranium recovery from phosphoric acid by solvent extraction method, where the
extracted OM coagulated and accumulated in large quantities at the interfacial area
between organic solvent and wet phosphoric acid as ‘crude’. The crude formation leads
to solvent losses which affect significantly the process economy [11].
About 95% of wet phosphoric acid is utilised in fertiliser application. Therefore, the
dissolved organic matter (DOM) in phosphoric acid is considered a serious problem with
regard to environmental and human health concerns where DOM can bind or complex toxic
metals during the application of phosphoric acid as fertiliser. Accordingly, several efforts
have been done regarding the removal or reduction of OM of their potential risk to public
health [12,13]. Most of the adopted processes to achieve this task are mainly based on either
liquid-liquid extraction or adsorption on suitably chosen solid materials [5–10,14].
Activated carbon has been utilised efficiently to remove a broad spectrum of organic
compounds, for example aliphatic and aromatic hydrocarbons, from water [15–17]. In
phosphoric acid purification processes, activated carbon have been extensively investi-
gated for OM adsorption and/or heavy metal ions [10,18,19]. Adsorption of OM using
powder activated carbon (PAC) is a slow process, and the adsorbed amount of OM is far
below the equilibrium adsorption capacity of PAC during a normal contact time [20].
Modification of carbon surfaces by physicochemical methods has been studied in order
to attain an in-situ efficient heavy metals removal. Therefore, the increasingly stringent
environmental regulations can be highly reached [21]. Carbon surface can be modified
to develop desirable physicochemical properties via adequate choice of activation
procedures. Surface properties of carbon structures, such as charcoal, can be modified
using inorganic acids [22]. This modification mainly affects the surface chemistry of the
carbons and sometimes alters their porosity and specific surface area [23]. The present
contribution aims to investigate OM sorption from commercial phosphoric acid onto
acid sites-modified charcoal through batch kinetics as well as equilibrium studies.

2. Experimental
2.1. Materials and reagents
HNO3 and HCl, chemical activating reagents, were supplied from ADWIC, Egypt. A granular
bio-charcoal (BC) was used as the base adsorbent. The BC was produced via an adiabatic
thermal conversion process of a type of solid waste namely; rice-straw. The conversion
process was carried out at 250°C for an operational time of 2 h [24,25]. Charcoal granules
were crushed into particles of 250–420 microns in size. The particles were then dried at 110°
C for 48 h in order to get them ready for the adsorption process. Another adsorbent was
parallel produced via treating a part of charcoal by HNO3. The treatment (leaching/oxida-
tion) step was achieved in a 500 mL Teflon flask. An amount of charcoal (30 g) and 200 mL
nitric acid (NAC) (6 M) were inserted into the bottle and were heated up at 70°C for 6 h. The
 INTERNATIONAL JOURNAL OF ENVIRONMENTAL ANALYTICAL CHEMISTRY 1213

solid particles were filtered, washed several times by distilled water and were next dried at
110°C for 48 h [26]. Such treated sample was named NAC. In order to obtain hydrochloric
acid (HAC) activated charcoal, as another acid activated structure, a part of the blank BC
sample was then treated with 100 mL hydrofluoric acid (2 M) for 6 h at 70°C. The gained
particles were next filtrated, washed with distilled water many times then introduced for
drying for 48 h at 110°C. The finally obtained adsorbent was labelled as HAC [26].
Crude di-hydrate phosphoric acid, the utilised during this investigation, was supplied
from Abu Zaabal Company for Fertilizer and Chemical Materials (AZFC). The chemical
analysis of the stated crude phosphoric acid is presented in (Table 1).

2.2. Apparatus
The purification of phosphoric acid was investigated in a cylindrical reactor of 500 mL
capacity and 10 cm diameter. The reactor is placed in thermostatically controlled water
bath and fitted with Teflon-coated stirrer (its diameter is 2 cm). The impeller tip speed
was adjusted to 200 rpm. The filtration of adsorbents from the cleaned acid have been
achieved using vacuum pump, Buchner type filter (its diameter is 4.6 cm) as well as
polypropylene filter with 177 microns aperture size.

2.3. Adsorption procedures

Unless otherwise stated, OM sorption process has been achieved in a thermostated
shaker bath at (25 ± 1°C) by shaking 1 g of BC or acid activated charcoal samples with
100 mL of the crude phosphoric acid. All experiments were performed in triplicate and
the mean values have been presented. The concentration of OM in phosphoric acid was
determined using spectrophotometer at 418 nm [27] before and after the purification
process. The amount of OM sorbet onto the sorbents qe (mg/g) was calculated by the
following equation:
V
qe ¼ ðCo Ce Þ
m

Table 1. Chemical composition

of crude phosphoric acid pro-
duced by di-hydrate process.
Element Phosphoric acid
Composition wt.%
P2O5 ≈ 23.5
SO4 3.35
CaO 0.34
F 0.64
Fe2O3 1.1
SiO2 0.03
MgO 0.8
Trace elements (ppm)
Mn 580
Pb 55.3
Zn 275
U 40
1214 M. H. TAHA ET AL.

where Co and Ce are the initial and equilibrium concentrations of the OM (mg/L),
respectively, m is the utilised sorbent weight (g), and V is phosphoric acid volume (L).
OM sorption efficiency was calculated from the following equation:
Co Ce
Organic matter sorption % ¼ 100
Co
The distribution coefficient (Kd) of OM between phosphoric acid and sorbent has been
obtained from the following relation:
Co Ce V
Kd¼ 
Ce m

2.4. Characterisation tools

The following analyses have been carried out for the prepared BC, hydrochloric, and NAC
activated charcoal: X-ray diffraction (XRD) for all sorbent samples had been achieved using a
Brucker AXS-D8 Advance (Germany) with Cu Kα radiation (λ = 1.5405Å) at a generator
voltage of 30 Kev and current of 40 mA. FT-IR analysis of the freshly made materials was
obtained in the range of 400–4000 cm−1 in KBr disc (ATI Mattson Genesis series, Model 960
M009 series. The surface as well as the cross-section morphology of the presented activated
carbon supported nickel membrane was carried out by an electron microscope model JM-
2100-XX, JEOL -Japan. This type of microscope offers as high magnification as 35,000 times.
TEM images in the present work were performed using JEM 2100 (JEOL, Japan) which offers
high-resolution electron imaging up to 0.143 nm and magnification as high as 1.5 million
times. The N2 BET surface area of the different carbonaceous materials was measured at 77 K
and 0.85 atmospheres (Coulter analyser, model SA 3100).

3. Results and discussion

In this research work, solid-waste-generated BC was synthesised via the thermal con-
version route. This carbonaceous species were then acid functionalised using both
hydrochloric and NAC. The acid-treated charcoals were then forwarded for organic
pollutants sorption from industrial di-hydrate phosphoric acid. The characteristics of
the either the blank BC or its acid activated species are next illustrated in details.

3.1. Characterisation of carbonaceous products

The obtained BC species from the thermal pyrolysis of rice-straw were collected and were
then forwarded for analysis. The structural and morphological characteristics of the
obtained bio-carbon are presented in Figures 1 and 2. The presented XRD spectrum in
Figure 6 shows a bit broad peak centred between 2θ of 18 and 26o with quite low-intense
sharp peaks embedded can be detected through the displayed spectrum. These peaks are
indicative to mixed structures of both amorphous and crystalline carbons. Another two
strong sharp signals at 2θ = 28 and 41 referring to crystals of silica and a mixed phase (Ti Al05
Si1.5 O4), respectively [28], can be also seen in the shown spectrum. The observation of
crystalline alumina and silica in the obtained carbon rather than their amorphous structure
 INTERNATIONAL JOURNAL OF ENVIRONMENTAL ANALYTICAL CHEMISTRY 1215

Figure 1. XRD pattern of the obtained carbon species at the optimum operating conditions of the
pyrolysis process.

Figure 2. FT-IR spectrum of the obtained carbon species at the optimum operating conditions of the
pyrolysis process and its sub-driven hydrochloric and nitric acid activated carbon.

in the feedstock is attributed to removal of the amorphous organic constituents during the
thermal process.
The structural properties of the BC as well as the acid activated carbon species have
been further illustrated through the presented FT-IR spectrum in Figure 2.
In the first region of absorption, a wide band with a reasonable intensity can be
noticed at 3600–3800 cm−1 [29]. This band peak is due to O–H stretching mode of both
the hydroxyl groups and adsorbed water which might exist in the given structure. In
addition, it must be indicated that the bands in the range of 3900–3650 cm−1 have also
been referred to the occurring hydrogen bonding between the OH groups [30].
For the second major absorption, the noted peak at 1640 cm−1 is indicative to the amides
that can be distinguished on the surface of the activated bio-carbons. The presence of such
1216 M. H. TAHA ET AL.

functional group could be obtained during the thermal conversion process owing to the
presence of primary amines that in the biomass based feedstock. The peak at approximately
1100 cm−1 belongs to the fingerprint of this carbon. This band can also be associated with
C–O symmetric and asymmetric stretching vibration of –C–O–C– ring [31]. The third region
show peak at 628 cm−1 is assigned to the C–H bending mode. The region in between 700–
900 cm−1 contains various bands related to C–H bending with different degrees of substitu-
tion [32]. The bending region for the activated carbon might indicate that the existing
aliphatic C–H is mainly as – CH2–. This in turn can clarify that most of the aliphatic structures
in the bio-carbon are cyclic structures.
IR spectra of the activated charcoal by both HCl and HNO3 acids confirm the addition
of acidic groups in each case, in comparison to the given spectrum of blank bio-carbon.
In general, the presented FTIR spectra reflect the differences between the two presented
structures. The activation by the two acids showed additional bands than that of the
blank carbon. Furthermore, the intensity of the band at the same wavenumber is lower
in the case of the acidified carbon than that of the as-prepared carbon. This can be
attributed to the increase in the number of acid sites to the structure which could
subsequently enhance the potential hydrogen bonding along the surface of treated bio-
carbon. In addition, Indicative absorption bands for the HCl molecules could be noticed
at 460 and 770 cm−1. This in turn had resulted in a subsequent change in the chemical
functional groups at each activation stage which could probably affect their separation
activity towards the OMs, as clearly illustrated in Section 3.
The inner as well as the surface morphology of the as-prepared bio-carbon structure
is illustrated throughout the exhibited TEM micrographs and SEM images in Figures 3
and 4, respectively.
The TEM images show amorphous morphology of overlapped carbon sheets. In an
agreement with the XRD pattern, embedded crystalline structures on the carbon sheets
can be observed. The surface morphology, Figure 4, has been in a match with the
acquired morphology in the TEM micrographs.

Figure 3. TEM micrographs of the illustrated carbon structure in Figure 1.

 INTERNATIONAL JOURNAL OF ENVIRONMENTAL ANALYTICAL CHEMISTRY 1217

Figure 4. SEM images of the illustrated carbon structure in Figure 1.

Particularly, non-smooth way surface has been detected for the surface of the
produced BC. Well-organised parallel micro-channels can be observed along the whole
structure of displayed surface. Moreover, moderate porous structure can be noticed
through the shown channels. This may obviously refer to the expected high adsorption
by the presented bio-carbon structure.
On the other hand, the texture properties of the acid treated carbons have been
discussed via both the surface area values and the given SEM images in Figure 5. For
the blank bio-carbon, the specific surface area value was found to be 900 m2/g while an
explicit reduction in the values of surface area could be noted after adding the acid sites.
Numerically, the surface area values were, respectively, reduced to reach 750 and 580 m2/
g for the case of attaching HCl and HNO3 to the bio-char. This can be attributed to the
coverage of a part of the carbon surface as well as the filling of its pores by the molecules
of both acids [33]. The detected decrease in the surface properties in the acid treated
carbon had been further confirmed via the exhibited SEM images in Figure 5.
It can be clearly seen that the addition of both HCl and HNO3 molecules to the carbon
structure had resulted in the increase of surface roughness in both cases. However,
stronger level of roughness can be noticed in the case of loading NAC in comparison to
that of HAC loading. In addition, the level of porosity has been much lower in the case of
nitric than in the other case. This can be referred to the high-potential accumulation of the
NAC molecules due to their strong physical interaction together as a result of its increased
number of electrostatic charge. The tetragonal molecules geometry of NAC may be
another reason for the surface roughness of the NAC structure.

3.2. Batch investigation

OM adsorption from crude dehydrate phosphoric acid, 23.5% P2O5, has been investi-
gated by using blank BC, HAC and NAC functionalised charcoals. The effect of sorbent
amount, reaction time, phosphoric acid concentration, and temperature on the OM
adsorption has been studied.
1218 M. H. TAHA ET AL.

Figure 5. SEM for (I) hydrochloric acid-activated charcoal and (II) nitric acid activated charcoal.

3.2.1. Effect of shaking time

The adsorption kinetics of OM, 780 ppm, from crude phosphoric acid by BC, HAC,
and NAC were studied to evaluate the obtained data and find out the controlling
mechanism of the adsorption. Therefore, the OM adsorption efficiency was investi-
gated at different time intervals, ranged from 15 to 480 min. The results of OM
adsorption kinetics are shown in Figure 6. It was found that the adsorption of OM by
BC, HAC, and NAC had increased by increasing stirring time till a steady state was
reached, 120 min; hence, no significant variation in the sorption percent had been
observed by then. This can be attributed to the coverage of adsorbent particles
surfaces by a mono-layer of the OM, up to the stated time [12,13]. Thus, no further
adsorption could take place by the adsorbents.
 INTERNATIONAL JOURNAL OF ENVIRONMENTAL ANALYTICAL CHEMISTRY 1219

3.2.2. Effect of adsorbent amount

The influence of sorbent amounts, ranging from 0.25 to 3.0 g/100 mL, on the removal of
OM from the impure acid was investigated. Other operating factors were kept constant
(reaction time of 120 min, stirring speed of 200 rpm, and room temperature). The
obtained data of OM adsorption % versus the increase of adsorbent amounts are plotted
in Figure 7. The obtained results clear that, the increase in amount of added carbon from
0.25 to 1 g/100 mL has been joined with an increase in the percent of OM adsorption;
for the three adsorbents (BC, HAC, and NAC). The subsequent increase in the adsorbent
amount, from 1 to 3 g/100 mL, has almost no effect on their efficiency towards OM
adsorption. This can be referred to those the corresponding structures among the OM
molecules which can efficiently interact with the adsorbents [13,14]. So that a dose of
adsorbent equal to 1 g/100 mL could be sufficient to provide the needed active sites to

Figure 6. Impact of stirring time on organic matter adsorption percent, % (1.0 g BC, HAC, and NAC/
100 mL of 23.5% P2O5 crude phosphoric acid at 25 ± 1°C, and 200 rpm).

Figure 7. Effect of solid/liquid ratio on the organic matter adsorption % from 23.5% P2O5 crude
phosphoric acid using BC, HAC, and NAC at 25 ± 1°C and 200 rpm.
1220 M. H. TAHA ET AL.

neatly eliminate such structures. Therefore, the liquid/solid ratio has been fixed at 1.0 g/
100 mL for the forthcoming steps of this investigation.

3.2.3. Impact of mechanical stirring speed

Mechanical stirring speed influence on OM adsorption process from di-hydrate phos-
phoric acid using BC, HAC, and NAC was achieved for various mechanical stirring speeds
ranging from 200 to 500 rpm at the optimum condition from the prior stages and at
room temperature. The experimental data are presented through Figure 8 as the
variation of OM adsorption efficiency with mechanical stirring speed variation. It can
be seen that the increase of stirring speed from 200 to 500 rpm had in turn slightly
elevated the efficiency of OM adsorption for BC, HAC, and NAC. The observed limited
increase might be referred to the better diffusion of the adsorbent particles within the
molecules of phosphoric acid [12]. However, since the adsorption increase is not highly
significant, 200 rpm was then chosen as a stirring rate for the next stages of this study.

3.2.4. Impact of phosphoric acid concentration

In the current stage, the prepared structures (BC, HAC, and NAC) were used for the OM
adsorption from phosphoric acid with different concentrations. In practical, concentra-
tions ranging from 29.5 to 45% P2O5, 120 min. shaking time, solid/liquid ratio, 1 g/
100 mL, stirring speed of 200 rpm and room temperature were utilised during this stage.
The collected experimental results are plotted in Figure 9. As clearly seen, the increase of
phosphoric acid concentration from 29.5 to 45% P2O5 was escorted by a decline in the
OM adsorption efficiency. Specifically reductions in the adsorption efficiencies from 41.9
to 13.9, from 67.2 to 23.6 and from 60.2 to 10.1% were noticed for BC, HAC and NAC,
respectively. The reason behind the noted decrease could be likely to the increase in the
number of the phosphoric acid molecules by increasing its concentration.
This in turn could result in the accumulation of the excess of the acid molecules over
the surface of the adsorbent particles. Consequently, a mono coverage layer of the acid

Figure 8. Influence of stirring speed on organic matter ion adsorption percent, % (room tempera-
ture, reaction time 120 min; 1.0 g BC, HAC, and NAC/100 mL crude phosphoric acid, 23.5% P2O5).
 INTERNATIONAL JOURNAL OF ENVIRONMENTAL ANALYTICAL CHEMISTRY 1221

Figure 9. Impact of acid concentration on organic matter adsorption percent onto BC, HAC, and NAC; 1 g
carbon/100 mL commercial phosphoric acid; reaction time 120 min.; room temperature; 200 rpm).

had been formed over the active site of the adsorbent. Therefore, limited adsorption
capability can be attained by the carbonaceous adsorbents.

3.2.5. Effect of the temperature

The effect of temperature on OM adsorption from commercial phosphoric acid, 23.5%
P2O5, onto BC, HAC, and NAC was investigated in the range 25–50 ± 1°C while imple-
menting the gained optimum operational conditions from the previous stages of this
work. The achieved data are exhibited in Figure 10 as a relation between OM adsorption
percent and temperature increase. The displayed data in Figure 11 indicates that the
temperature increase had a positive impact on OM adsorption efficiency. Numerically,
the variation of temperature from 25 to 50°C could increase the adsorption efficiency
from 41.7 to 54.3% for C, from 67.3 to 90.1% for HAC and from 60.1% to 79.7% for NAC.
The increase of adsorption efficiency by the temperature increase is attributed to the
ability of the acid particles to depart from the media to the adsorbent surface, hence
better adsorption process can be observed [10].

3.3. Sorption kinetic modelling

Sorption is performed as an operation, either in batch or continuous mode, in a column
packed with porous sorbents. The study of adsorption kinetic is important in the solid/
liquid systems because it provides important information on the mechanism of adsorp-
tion process as well as the rate of reaction and.
The sorption process can be described based on the following sequential stages (i) solute
transportation in the solution bulk; (ii) solute diffusion across the liquid film surrounding
sorbent particles; (iii) solute diffusion along the pore walls (intraparticle diffusion); (iv)
adsorption and desorption of solute molecules on/from the sorbent surface. The sorption
rate could be mainly controlled by any of these stages or a combination of a few stages
[34,35]. The rate-controlling step may be varying during the sorption process [36].
1222 M. H. TAHA ET AL.

In the past decades, different mathematical models were proposed for describing the
sorption results. These models could be classified as adsorption reaction models and
adsorption diffusion models. Both types of models are used to describe the kinetic of
sorption process; though, they are quite different in nature [37]. In this regards,
Lagergreen first-order and pseudo-second-order rate equations (as an example for
adsorption reaction models), and Morris–Weber equation (as an example for adsorption
diffusion models) were applied to analyse the adsorption kinetics of OM adsorption from
industrial di-hydrate phosphoric acid onto BC, HAC, and NAC carbon at 25 ± 1°C.
Lagergreen first-order equation can be written as follows [38]:
00
dqt00 =00 dt00 ¼ kp1 ðqe  qt Þ (1)

Figure 10. Influence of reaction temperature on organic matter adsorption percent (1.0 g BC, HAC,
and NAC/100 mL phosphoric acid, 23.5% P2O5; time 120 min; 200 rpm).

Figure 11. Lagergreen plots for organic matter sorption from di-hydrate crude phosphoric acid,
23.5% P2O5, onto BC, HAC, and NAC.
 INTERNATIONAL JOURNAL OF ENVIRONMENTAL ANALYTICAL CHEMISTRY 1223

where qe is the concentration of the OM sorbed at equilibrium (mg/g), qt is the

concentration of the OM sorbed at time t (mg/g) and K1 is the overall rate constant.
Integrating Equation (1) with the boundary conditions of qt = 0 at t = 0 and qt = qt at
t = t, yields:
k1
logðqe  qt Þ¼ logqe  t (2)
2:303
The pseudo-second order is expressed as follows [39]:
00
dqt00 =00 dt00 ¼ k2 ðqe  qt Þ2 (3)

where K2 is the rate constant of pseudo-second-order equation (g/mg. min)), and the
products K2qe2 is the initial sorption rate represented as h. For the boundary conditions
t = 0 to t = t and qt = 0 to qt = qt, the integrated form of Equation (3) can be written as
 
t 1 1
¼ þ ðtÞ (4)
qt k2 q2e qe

The initial adsorption rate, h (mol g−1 h−1), was calculated from Equation (5), while
Equation (6) was used to determine the half-equilibrium time, t1/2 (h) [40,41]:

h ¼ k2 q2e (5)

1
t1=2 ¼ (6)
k2 qe

The scatter plot of log (qe – qt) versus time (Figure 11) shows the result of the
correlation coefficient of OM adsorption in the pseudo-first-order kinetic model. The
correlation coefficients (R2) value, the overall rate constant K1, and the value of qecal for
BC, HAC, and NAC carbon have been tabulated in Table 2. The kinetic plot of t/qt versus
time for OM sorption onto C, HAC, and NAC are represented in Figure 12. The kinetic
parameters of this model are calculated from the slope and intercept of the linear plots
and are given in Table 2.
According to the analysis result as shown in Table 2, adsorption process of OM was
not followed pseudo-first-order kinetic model for the applied carbon sorbents (BC, HAC,
and NAC) where the R2 values are not high especially for BC and NAC carbons. In
addition, the theoretically calculated equilibrium sorption capacity, qecal, values for the
applied three carbons types are not in agreement with the experimental sorption
capacities qeexp values.

Table 2. The calculated parameters of the pseudo-first-order and pseudo-second-order kinetic

models.
Lagergreen pseudo first-order Pseudo second-order
qecal qee xp qecal qee xp h (mol t1/2
K1 (min −1) (mg/g) (mg/g) R2 K2 (min −1) (mg/g) (mg/g) g−1 h−1) (h) R2
BC 0.016 16.5 33.6 0.89 0.0019 34.8 33.6 2.3 15.4 0.99
HAC 0.015 20.2 53.7 0.83 0.0017 55.2 53.7 5.0 11.0 0.99
NAC 0.020 34.4 47.9 0.87 0.0008 50.8 47.9 2.1 21.3 0.99
1224 M. H. TAHA ET AL.

Figure 12. Pseudo-second-order plots for adsorption of organic matter from di-hydrate crude
phosphoric acid, 23.5% P2O5, using BC, HAC, and NAC.

In regards to pseudo-second-order model, it is observed that the values of correlation

coefficients (R2) are (0.99) and the calculated sorption capacity (qe) at equilibrium is in
good agreement with the experimental sorption capacity. Accordingly, the sorption of
OM onto BC, HAC, and NAC followed the pseudo-second-order kinetic model. This
means that the sorption rate constant is controlled by chemical sorption process [42]
and involved the exchange of electrons between the organic structures and adsorbents
[43]. Moreover, it is clear that the adsorption capacity follows the order of HAC > NAC >
BC. This indicates that the charcoal activation with hydrochloric and NAC enhances the
adsorption properties of the charcoal. In addition, the results obtained in Table 2 clear
that the initial sorption rate increased from 2.3 mol g−1 h−1 in case of BC to 5 mol g−1 h−1
in the case of HAC. However, the half-equilibrium time decreased from 15.4 h in the case
of BC to 11.0 h in the case of HAC, which prove the positive effect of HAC on the
adsorption characteristics of commercial granular charcoal.
A comparison between the adsorption capacity of blank and acid activated bio-char
(present work) and some other sorbents, available from the literature, for OM recovery
from phosphoric acid is presented in Table 3. It can be clearly seen that the presented
carbon structures in this study have heavily scored. Numerically, the blank bio-char had
shown at least 1.5 adsorption capacity higher than the given adsorbents from literature.
The adsorption capacity had then significantly increased via using the acids activated-
carbons. Specifically, the adsorption capacities could increase to the double of the given
highest adsorption capacity of the presented other adsorbents (Table 3).
Intra-Particle Diffusion-Controlled Adsorption (Morris–Weber model) has been applied
to investigate the internal diffusion mechanism during the adsorption of OM from di-
hydrate phosphoric acid onto BC, HAC, and NAC. Weber–Morris found that in many
adsorption cases, solute uptake varies almost proportionally with t0.5 rather than with
the contact time t [44]:

qt ¼ki t0:5 þB (7)

 INTERNATIONAL JOURNAL OF ENVIRONMENTAL ANALYTICAL CHEMISTRY 1225

Table 3. The experimental capacity of blank and acid activated bio-char compared with
the sorption capacity of some other sorbents for OM recovery from phosphoric acid.
Sorbent type Sorption capacity, (mg/g) Refs.
Low quartz kaolinite (Ball clay) 11.7 [1]
High quartz kaolinite (Kaolin clay) 5.7
Raw bentonite clay (RBC) 17.2 [15]
Raw grey clay (RGC) 15.0
Natural bentonite 24.0 [40]
Sulfuric acid-activated bentonite 27.7
Hydrochloric acid activated bentonite 17.3
Blank bio-char (BC) 33.6 Present work
Hydrochloric acid-activated bio-char (HAC) 53.7
Nitric acid-activated bio-char (NAC) 47.9

Figure 13. Morris–Weber illustration for OM adsorption from crude phosphoric acid, 23.5% P2O5,
using BC, HAC, and NAC.

Table 4. Kinetic parameters of Morris–Weber model for OM adsorption onto

BC, HAC and NAC.
Ki (mg/g min1/2) B (mol/g) R2
BC Stage I 2.07 10.02 0.96
HAC 2.61 23.7 0.99
NAC 3.7 5.2 0.97
BC Stage II 0.09 31.6 0.99
HAC 0.1 51.3 0.97
NAC 0.07 46.3 0.98

According to Equation (7), the relation between q vs. t0.5 should give straight line (Figure 13).
kid and B constants were calculated from the slope and intercept, respectively, and pre-
sented in Table 4. Generally, Kid increases by increasing the initial adsorptive concentration
[45,46]. For kinetics controlled only by Intra-Particle Diffusion model, B should equal 0,
meaning that the linear relationship forced through the origin [47,48]. However, in most
studies, this relationship shows multiple mechanisms (Multilinearity relatioship) that control
the process and provides better fit when B > 0, meaning not pass through the origin [49–51].
1226 M. H. TAHA ET AL.

Each linear part is representing a controlling mechanism. In the first stage, instanta-
neous adsorption or external surface adsorption occurs. In the second stage, Intra-
Particle Diffusion model begins, and in the third stage, the sorption process approaches
equilibrium. The sorption process slows as surface coverage reaches saturation. Defining
the time period for each line segment, based on the kinetic data, is somewhat arbitrary,
so piecewise linear regression could help in this case [51].
The obtained results showed that the intraparticle diffusion had two regions for OM
adsorption onto granular and acid activated charcoal sorbents. The high adsorption rate
in the first region was attributed to the high concentration of metal ions in solution and
more sorption sites on the adsorbent surfaces. The second region, the adsorption rate
slow, was the rate-determining step. This is because most of the adsorption sites on the
adsorbent surfaces were occupied by OM [41]. Moreover, from Figure 8 it is clear that
the plots are not linear in the whole range of contact time for the applied three sorbents
(BC, HAC, and NAC); therefore, the intraparticle diffusion was not the only mechanism of
OM adsorption from di-hydrate phosphoric acid.

3.4. Sorption thermodynamics

Thermodynamic analysis of the sorption system is very important to predict if the
sorption process is possible or not. In this respect, the thermodynamic parameters,
namely the Gibbs free energy (ΔG), the enthalpy (ΔH) and the adsorption entropy (ΔS)
for the OM adsorption from industrial phosphoric acid onto granular, hydrochloric and
NAC activated charcoal were evaluated.
At equilibrium, Van’t Hoff equation could be used to evaluate Gibbs free energy (ΔG)
at constant temperature as follows [52]:
ΔG ¼ 2:303 RT log kd
where R is the universal gas constant, T is temperature in kelvin (K), and Kd is the
adsorption equilibrium constant at 25°C.
To predict enthalpy change (ΔH) and entropy change (ΔS), Van’t Hoff reformulated in
terms of the equilibrium constant (Kd) as follows:
DH 1 ΔS
logkd ¼   þ
2:303 R T 2:303 R
The enthalpy change (ΔH) and entropy change (ΔS) are also related to the free energy
change (ΔG) at constant temperature by the relation:
ΔG ¼ ΔH  TΔS
The plot of logKd versus 1/T should give linear relationship (Figure 14), the slope and intercept
of this relationship could be used to evaluated (ΔH) and (ΔS) for OM sorption process.
The thermodynamic parameters of OM sorption from crude phosphoric acid onto BC,
HAC, and NAC are presented in Table 5.
The obtained data in Table 5 show that the enthalpy change (ΔH) values were
positive, which confirmed the endothermic nature of OM adsorption onto granular
and acid activated carbon. The negative values of free energy change (ΔG) for the OM
adsorption process clear that the adsorption process onto granular and acid activated
 INTERNATIONAL JOURNAL OF ENVIRONMENTAL ANALYTICAL CHEMISTRY 1227

Figure 14. Relation between log Kd and 1/T for organic matter adsorption from di-hydrate phosphoric
acid using BC, HAC, and NAC.

Table 5. Thermodynamic parameters for OM sorption from commercial di-hydrate phosphoric acid
using BC, HAC, and NAC.
ΔG (kJ/mol) ΔH ΔS
25°C 30°C 40°C 50°C (kJ/mol) (J/mol K)
BC −14.95 ± 0.02 −15.37 ± 0.02 −16.10 ± 0.02 −16.91 ± 0.02 8.22 ± 0.04 33.90 ± 0.2
HAC −16.13 ± 0.04 −16.60 ± 0.04 −17.44 ± 0.04 −18.27 ± 0.04 9.20 ± 0.01 37.07 ± 0.3
HNC −15.85 ± 0.04 −16.45 ± 0.04 −17.22 ± 0.04 −18.04 ± 0.04 9.54 ± 0.03 37.24 ± 0.2

charcoal was a spontaneous process. Moreover, by increasing the reaction temperature,

more negative value of ΔG were obtained, meaning that OM sorption process is more
promising at higher temperatures [53]. The positive value of (ΔS) shows that the system
entropy increased during the sorption process. However, the entropy of the universe
(including the system and its surroundings) could increase due to the sorption reaction
was not an isolated process.

3.5. Mechanism of organic matter adsorption

Adsorption isotherms obtained for three adsorbents have same chemical structures; how-
ever, two of them had been modified via the loading of acid sites onto their particles. The
suggested mechanism during this research work is highly relevant to the presence of HA
molecules within the content of the feedstock (commercial phosphoric acid). The sorption
of OM on the introduced particles of activated bio-char is strongly related to divalent metal
concentration, ionic strength, or decreasing of solution pH [54–56]. The increases of adsorp-
tion capacity are partly attributed to physical reduction in macromolecule size, which arises
in solution previous to adsorption. Nevertheless, the neutralisation of charge on OM
molecules in the adsorbed state may also be significant [57]. Therefore, the presence of
calcium salts in feedstock could neutralise the electrostatic repulsion between OM and the
sorbents forming an adsorbent–salt–adsorbate complex; thus, adsorption of OMs takes
place [58,59]. Li et al. [59] also stated that the influence of Ca (II) depends on the source
1228 M. H. TAHA ET AL.

of the OM species in the tested sample. Hence, the sorption capacity for a commercial OM
enhanced by increasing Ca(II) concentration.
In the current research work, the increased adsorption capacity of OM due to
pulverisation might be in relevance to high Ca (II) concentration in the treated grade
of phosphoric acid. Accordingly, the occurrence of cations, specially multivalent cations
such as Ca(II), could result in increasing the adsorption capacity of OM in general and HA
particularly. In addition, the presence of high concentrations of different cations in the
phosphoric acid sample could potentially play an important role in adsorption of OM
species. Specifically, the penetration of these cations into the pores of the presented
carbonaceous adsorbents working sample producing aggregates could probably attract
the species of OM. These species might then enter the pores where the cations
aggregates had enhanced the accumulation of OM. This hypothesis could be continued
until the OM species could not diffuse further into pores of bio-char based adsorbent
once these pores are blocked.
The particulates of OM could have gathered by them in the vicinity of the adsorbents
outer surface. Based on this hypothesis, the maximum quantity of adsorbed OM species
should controlled by the adsorbent external surface area that exposed to the bulk solution,
as reported in 2010 by Ando and co-workers [54]. Unlike the latter statement by Ando et al.,
the current research work suggests a new approach in the mechanism of OM species
adsorption onto bio-char-based adsorbents. Particularly, the relationship between the
adsorption capacity of adsorbents and their surface area had shown different trend.
In this work, although the blank bio-char (BC) had higher surface area than both HAC
and NAC, it showed less adsorption capacity. This could be attributed to both the
capability of both HAC and NAC to attain hydrogen bonding during the process of
adsorbing the species of OM. However, the enhanced adsorption capacity of HAC over
the NAC structure could be likely referred to two reasons. The first one belongs to the
geometry of both HCL and HNO3 that were used as activators for the bio-char. The HCL
has linear geometry while the NAC has a tetrahedral one. Therefore, the ability of HCl to
perform a hydrogen bonding than the NAC since its particles could easily accumulate
over each other. The second reason behind the higher adsorption capacity of HAC than
that of NAC is the slightly less surface area of the latter structure than the other one.
The increased capability of both HAC and NAC to adsorb the OM species has been
further confirmed via the presented SEM images (Figure 15 I–II) of their spent adsorbent
after the process of OM adsorption. Furthermore, the ability of both structures; HAC and
NAC, to perform hydrogen bonding has been proved through the given IR spectra for
the spent adsorbents, Figure 16 (I–II).
In reference to the displayed SEM images in Figure 15, the morphologies of the two
presented carbons structures, as adsorbents, in this study have strongly changed. The
surface of both bio-char-activated structures had been totally with amorphous particles.
These changes in morphologies are mainly due to the increased efficiency of the two carbon
structures in adsorbing the organic pollutants from the phosphoric acid. Alongside with the
surface morphology, the given IR spectra in Figure 16 had verified the efficient removal of
organic species from phosphoric acid sample. Particularly, the intensity and broadness of
detected IR bands in the freshly made NAC and HAC have been strongly increased in their
spent adsorbents after the removal process. Furthermore, some additional peaks in the
range of 1400–1800 cm−1 that did not exist in the as-prepared structures could be noticed.
 INTERNATIONAL JOURNAL OF ENVIRONMENTAL ANALYTICAL CHEMISTRY 1229

Figure 15. SEM for (I) hydrochloric acid activated charcoal and (II) nitric acid activated charcoal after
OM adsorption process.

This can be as result of the uptake of the different OMs onto the surface of the spent
adsorbents. On the hand, the appearance of absorption band at 497 cm−1 in spectra of both
structures is indicative to hydrogen bonding of NAC and HAC with adsorbed OMs onto their
surfaces. This consequently may verify the suggested removal mechanism of OMs, as earlier
illustrated through this section.

3.6. Developed phosphoric acid pre-treatment for process scale up

According to the above-mentioned results – for the industrial phosphoric acid clarifica-
tion using BC, HAC, and NAC charcoal – it is indicated that the favoured experimental
parameters were as follows: room temperature, reaction time of 120 min, and sorbent
dosage of 10 g/L. With regard to these preferred parameters, the crude phosphoric acid
1230 M. H. TAHA ET AL.

Figure 16. FT-IR absorption bands for hydrochloric and nitric acid activated charcoal before and after
OM adsorption process.

clarification efficiency was 41.7% for granular charcoal, 67.2 for HAC activated charcoal,
and 60.1% for NAC activated charcoal.
Based on the aforementioned investigations, a process for commercial phosphoric
acid, 23.5% P2O5 treatment batch-wise with HAC activated carbon was developed. In this
respect, 1.0 l of crude phosphoric acid was treated with 10 g of HAC for 120 min at room
temperature. Subsequent filtration was occurred. The chemical analysis and the physical
properties of the treated di-hydrate phosphoric acid are given in Table 6.

3.6.1. Fixed-bed-based process of phosphoric acid purification

The fixed-bed column experiment was performed using a glass column (of 1 cm diameter
and 25cm in length) packed with 10 g of HAC carbon. The carbon adsorbent bed was wetted
with diluted pure phosphoric acid. The industrial di-hydrate phosphoric acid solution
(containing 780 mg/L OM) was passed through the column with a fixed flow rate of 2 mL/
min. The OM concentration in the eluted phosphoric acid was measured and the obtained
results are presented graphically as a relation between Ce/Co and phosphoric acid

Table 6. The chemical analysis

of the pretreated phosphoric
acid.
Element Phosphoric acid
Composition wt.%
P2O5 ≈ 23.5
SO4 3.02
CaO 0.21
F 0.60
Fe2O3 0.81
SiO2 0.03
MgO 0.7
Trace elements (ppm)
Mn 496
Pb 45.4
Zn 241
U 38
 INTERNATIONAL JOURNAL OF ENVIRONMENTAL ANALYTICAL CHEMISTRY 1231

Figure 17. Break through curve of carbon.

throughout volume as shown in Figure 17. From the figure, it is obviously clear that the
carbon saturation capacity (Ce/Co equal 1) was achieved after 14 mL phosphoric acid.
Therefore, based on the OM concentration in the phosphoric acid working sample is 780
ppm and the weight of HAC carbon used is 10 g, it is clear that the carbon used has been
almost saturated with 1.09 g OM/g of the sorbent.

3.7. Reusability of acid activated bio-char

The saturated HAC sorbents has been washed with hot distilled water and reused again for
OM adsorption from crude phosphoric acid. This process has been repeated for several
times to evaluate the reusability of HAC activated bio-char which showed the highest
adsorption efficiency. Figure 18 shows the reusability efficiency of HAC for OM sorption.
The obtained results clear that after five consecutive adsorption and desorption cycles, the
efficiency of HAC activated bio-char has become almost the same as the blank bio char
which could be attributed to the displacement of the HAC from the bio-char. This means
that, HAC could be applied successfully for 5 consecutive adsorption and desorption cycles.
After that the bio-char has to be introduced to acid activation process.
Taking in consideration the number of adsorption-desorption cycles and the energy
consumption during the preparation of carbon species, the presented carbon structures are
of high suitability of such application. The production of biochar through the pyrolysis
process could be attained at a processing time of 2 h and consuming 3 KWh using a thermal
element of power output equals 1500 W. therefore, extremely low energy consumption is
attached through the carbon synthesis step. Hence, an economic benefit is provided
through using such adsorbents for the purification of industrial phosphoric acid.

4. Conclusion
Biomass residual generated bio-char and its sub-produced acid activated charcoals have
been used for OM sorption from crude phosphoric acid, 23.5% P2O5. The adsorption onto
1232 M. H. TAHA ET AL.

Figure 18. Adsorption and desorption cycles for OM recovery using HAC.

the three carbonaceous structures (labelled as BC, HAC, and NAC) has reached equilibria
after 120 min of a processing time. Experimental results clarify that HAC activated carbon is
more effective than blank BC and NAC activated carbon towards the OM removal from
crude phosphoric acid. The obtained data were analysed through various kinetic models.
The acquired results have been successfully described by the pseudo-second order for blank
and acids activated bio-char. Thermodynamic investigation for the OM sorption process
indicated that the removal process had been of an endothermic behaviour. Simultaneously,
the thermodynamics parameters ΔH and ΔS were calculated and showed positive values
that could confirm the endothermic nature of the OM adsorption process. On the other
hand, ΔG was found to be negative value which refers to the execution of a spontaneous
process of pollutants removal.

Disclosure statement
No potential conflict of interest was reported by the authors.

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