Biomass Conversion and Biorefinery

https://doi.org/10.1007/s13399-020-00995-5

ORIGINAL ARTICLE

Microporous nano-activated carbon type I derived from orange

peel and its application for Cr(VI) removal from aquatic environment
Ahmed El Nemr 1 & Rawan M. Aboughaly 2 & Amany El Sikaily 1 & Safaa Ragab 1 & Mamdouh S. Masoud 2 &
Mohamed Shafik Ramadan 2

Received: 5 June 2020 / Revised: 21 August 2020 / Accepted: 2 September 2020

# Springer-Verlag GmbH Germany, part of Springer Nature 2020

Abstract
In this work, microporous nano-activated carbon (MNAC) was prepared from orange peel by chemical activation with zinc
chloride (ZnCl2). MNAC has been characterized by FTIR, BET, TGA, TEM, SEM, and EDAX analyses. The fabricated MNAC
has 1228.2 m2/g-specific surface area and was considered microporous nano-material. The MNAC has been tested for the
adsorption of hexavalent chromium from its aqueous solution. MNAC showed good adsorption behavior towards Cr(VI) ions
from aqueous environment. To achieve the optimum condition for the adsorption process, solution pH, time of reaction,
adsorbent dose, initial concentration of Cr(VI) ions, and solution temperature have been investigated. The maximum monolayer
capacity (133.33 mg/g) of MNAC was achieved at pH 1, 100-min reaction time, and 1.0 g/L adsorbent dosage. The pseudo-
second-order model described the kinetics of Cr(VI) ions adsorption (R2 > 0.9972). Isotherm results showed that both Langmuir
and Freundlich isotherm models are applicable to the batch experimental data, with the Langmuir model considered as the most
applicable model. Thermodynamic parameters explained that the process of adsorption is appropriate in nature, endothermic, and
spontaneous. The thermodynamic parameters, such as Gibb’s free energy (ΔG°), standard entropy (ΔS°), and standard enthalpy
changes (ΔH°), were estimated. The value of ΔG° was found to be negative for the adsorption of Cr(VI) ions, which confirmed
the feasibility and spontaneous probability of the adsorption process.

Keywords Activated carbon . Adsorption . Carbonization . Orange peel . Toxic chromium . ZnCl2 activation

Abbreviations
ΔG° Gibb’s free energy change
ΔH° Standard enthalpy change (kJ/mol)
* Ahmed El Nemr ΔS° Standard entropy change (kJ/mol)
ahmedmoustafaelnemr@yahoo.com; ahmed.m.elnemr@gmail.com BET Brunauer-Emmett-Teller analysis
C The intercept of intraparticle diffusion
Rawan M. Aboughaly C0 Initial Cr(VI) concentration (mg/L)
r.aboghaly@gmail.com
Ct Cr(VI) concentration at time t (mg/L)
Amany El Sikaily DTG Deferential thermal analysis
dramany_mas@yahoo.com
EDAX Energy dispersive X-ray analysis
Safaa Ragab F Fractional attainment of equilibrium (F = qt/qe)
Safaa_ragab65@yahoo.com FTIR Fourier transform infrared
Mamdouh S. Masoud h Initial adsorption rate
drmsmasoud@yahoo.com HCl Hydrochloric acid
Mohamed Shafik Ramadan IUPAC International Union of Pure and Applied
drmshafek@yahoo.com Chemistry
k1 Pseudo-first-order rate constant (L/min)
1
Environmental Division, National Institute of Oceanography and k2 Pseudo-second-order rate constant (g/mg min)
Fisheries, Kayet Bey, Elanfoushy, Alexandria, Egypt
K2Cr2O7 Potassium dichromate
2
Department of Chemistry, Faculty of Science, Alexandria University, KC The equilibrium constant
Alexandria, Egypt
 Biomass Conv. Bioref.

Kdif Rate constant of intraparticle diffusion (mg/g that has been studied for many years, yet we still urgently need
min1/2) other options and methods to address hexavalent chromium
KF Freundlich relative adsorption capacity and other toxic contaminants [1, 23, 24, 26, 27, 30, 32].
KFD Film diffusion rate constant Chemical precipitation [12, 36, 52, 54], filtration [11, 57],
KL Langmuir adsorption equilibrium constant (L/mg) electrochemical treatment [84, 90], reduction [81, 82], ion
MB Methylene blue exchange [6, 7, 40], membrane technology [2, 56, 93], evap-
MNAC Microporous nano-activated carbon oration removal [52], reverse osmosis [3, 45], and solvent
MP Micropore analysis extraction [75, 76, 91] are the most used methods for remov-
MW Molecular weight ing toxic metal ions from wastewater. However, most of these
pHZPC Zero point of charge processes have drawbacks including the incomplete metal re-
PSD Pore size distribution moval and high cost and the production of toxic sludge and
qe The adsorption capacities at equilibrium (mg/g) other disposal waste products [86]. Adsorption methods are
Qm Langmuir maximum monolayer adsorption (mg/ still widely used and are the most economical process for
g) removing toxic pollutants from wastewater. It is the most
QmF Freundlich maximum adsorption capacity (mg/g) widely used process for removing toxic metal ions from the
qt The adsorption capacities at time t (mg/g) aqueous solution [60, 61, 71, 72]. Several reports have already
R2 Correlation coefficients been published about producing low-cost adsorbents using
SBET Specific surface area (m2/g) cheaper and readily available materials [4, 21, 28, 31, 73,
SEM Scanning electron microscope 74]. Activated carbon is used in a wide variety of applications
t time (min) and has been proven to be a highly effective absorbent mate-
T Absolute temperature rial to remove a wide range of organic and inorganic pollutants
t1/2 The square root of time (min1/2) as well as gases from various media [22, 25, 77, 78]. Activated
TEM Transmission electron microscope carbon is classified based on its size into four different types:
TGA Thermogravimetric analysis granular, powder, clothe, and fiber. Each type of them has a
V Volume (L) specific application and also has advantages and disadvan-
Vm Micropore volume tages if used in wastewater treatment. Therefore, researchers
VT Total pore volume (cm3/g) continue to work to produce new types of low-cost activated
W The mass of adsorbent (g) carbon by searching for new inexpensive sources to be used in
ZnCl2 Zinc chloride the manufacture of activated carbon because commercial ac-
tivated carbon is still very expensive [21]. Adsorption can be
an effective method for removing toxic hexavalent chromium,
1 Introduction especially when combined with appropriate regeneration steps
to reduce processing cost. The use of adsorption method in
Water pollution is a major cause of concern for chemists and pollution treatment solves the problems of sludge disposal and
environmental engineers, especially due to heavy metals [20]. makes the treatment system more effective, especially eco-
The toxicity and accumulation of heavy metals across the food nomically, when low-cost adsorbents are used and can be
chain cause major environmental problems and therefore af- reactivated and reused again [34, 36, 37]. High surface areas,
fect the health of living organisms, especially human and an- microporous characters, and surface chemical natures of acti-
imal health [5, 59, 66]. Chromium compound is considered vated carbons have made them potential absorbent materials
one of the most dangerous inorganic pollutants. The state of for removing heavy metals from industrial wastewater. Low-
chromium valence is from 2 to 6+ but it is generally found as cost activated carbon adsorbents must be produced from use-
trivalent (Cr (III)) and hexavalent chromium (Cr (VI)) in nat- less, low-value, and readily available materials [43, 44, 49,
ural environments. Cr(III) and Cr(VI) are stable forms in the 50].
nature, whereas states of other valences are unstable and short- The annual global production from orange is estimated in
lived in biological systems [18, 19, 67]. Hexavalent chromium more than 68 million tones, and more than 2.7 million tones
is produced industrially when Cr(III) is heated in the presence represents Egypt’s production quantity from the world pro-
of mineral bases and atmospheric oxygen [83]. Trivalent chro- duction according to FAO in 2012. Orange peel consist of
mium in minimal concentration helps the human body to con- cellulose (13.61%), lignin (2.1%), hemicellulose (6.1%), and
trol blood sugar levels, while hexavalent chromium conceders ash (1.5 %) [85]. Orange peel is one of the worthless wastes
as a carcinogenic and mutagenic agent, and it is toxic to many that are disposed of from the juice industry and was used in
plants, aquatic animals, bacteria, and powerful epithelial irri- this study as a source for preparing a new microporous nano-
tant [63]. The study of hexavalent chromium removal activated carbon (MNAC) using the chemical activation meth-
methods is one of the most important environmental issues od by zinc chloride. The resultant activated carbon was found
Biomass Conv. Bioref.
to have high specific surface area and was applied to remove
Cr(VI) from its aqueous solutions. The effect of various pro-
cess parameters on the evolution of microporous structure was
investigated by different analysis techniques. Isotherm, kinet-
ic, and thermodynamic studies were investigated for Cr(VI)
adsorption by MNAC.
2 Materials and methods
2.1 Preparation of raw materials
Orange peel was collected from local market of Alexandria,
Egypt, and the collected orange peel was washed with tap
water to remove dirt, then with distilled water and oven dried
(105 °C for 24 h). The dried orange peel was crushed and
sieved for particle size fraction of less than 100 μm. Zinc
chloride (ZnCl2, MW 136.30 g, Assay 99.5%) and Starch
((C6H10O5)n were obtained from Universal Fine Chemicals
PVT-LTD, Mumbai, India. Sodium Nitrate (NaNO3, MW
84.99 g) was obtained from MERCK, Darmstadt. Iodine and
sodium thiosulfate (Na2S2O3.5H2O, MW 248.17 g, Min. Assy
99%) and 1,5-diphenylcarbazide as a reagent for Cr(VI) were
obtained from BDH chemicals LTD, England. Potassium di-
chromate (K2Cr2O7, MW 294.195 g) was obtained from
ADWIC, El-Nasr Pharmaceutical Chemical Company,
Egypt. Potassium iodide (KI) was obtained from Sigma-
Aldrich. Hydrochloric acid (HCl, M.W 36.46 g, Assay 30–
34%) was obtained from SD Fine-Chem Limited (SD FCL),
Mumbai, India.
2.2 Preparation of activated carbon
The dried orange peel (800 g) was impregnated with zinc
chloride solutions including 400 g of ZnCl2 in 1 L with ratio
2:1. After 24-h impregnation period, the mixture was
dehydrated for 24 h at 110 °C and then pyrolyzed in Quartz
cylinder 5.5 cm diameter and 60 cm length using a muffle
furnace (Tubular Furance Nabertherm B180 (RT 50/250/
13)) under the flow rate of nitrogen 50 mL/min at 700 °C
for 30 min holding time. The obtained activated carbon was
cooled to room temperature and then boiled in a solution of
3 M HCl and then filtered off, washed with distilled water
until washing solution contain no chloride. The final product
of activated carbon (MNAC) was oven dried at 70 °C over
night, then crushed and sieved to size smaller than 100 μm
and kept in glass bottle until used [77, 78].
2.3 Preparation of artificial wastewater
A stock solution of 1000 mg/L was prepared by dissolving
2.83 g of potassium dichromate (K2Cr2O7) in 400 mL and
completed to 1000 mL with double distilled water. The
standard curve of the hexavalent chromium concentration
reading was made using concentrations ranging from 10 to
150 mg/L prepared from the stock solution, and the higher
concentrations were measured by dilution. Double-distilled
water was used for preparing all of the reagents and solutions.
The solution pH values were controlled by addition of 0.1 M
HCl or NaOH. All the adsorption experiments were carried
out at room temperature (25 ± 2 °C) [31, 32].
2.4 Batch experiment
A batch adsorption experiments were employed to evaluate
the adsorption capability, thermodynamic, and kinetic param-
eters of MNAC. A series of Erlenmeyer flasks (300 mL) con-
taining 100 mL of different initial concentrations of Gr(VI)
ions solution (200–600 mg/L) and different amounts of
MNAC (1.0–3.0 g/L) were shaken at 200 rpm for a certain
time. The sample pH was adjusted to the desired values with
0.1 M HCl or NaOH before and during the experiments. The
concentration of Gr(VI) ions was determined by spectropho-
tometry (SPEKOL1300 UV/Visible ) using the method of
1,5–diphenylcarbazide as chromogenic agent (λmax = 540
nm) [19, 23]. The adsorption capacities at equilibrium (qe)
were calculated from Eq. (1):
c0 −ce
qe ¼ V ð1Þ
w
The effect of pH was studied for MNAC by using 100 mL
of 100 ppm of initial Gr(VI) ions concentration using solution
pH ranged between 1 and 6. The percentage of removal was
calculated by the equation (2):
C 0 −C t
Removal ð%Þ ¼  100 ð2Þ
C0
The effect of adsorbent dose, the kinetics, and the isotherm
studies for MNAC were performed using various initial con-
centrations of Gr(VI) ions solution (200–600 mg/L) using
different doses (1.0–3.0 g/L) at optimum pH. The reactions
mixture were shaken at 200 rpm, and the Gr(VI) concentration
was analyzed at different interval times at room temperature
(25 ± 2 °C).
2.5 Physical and chemical characterization of MNAC
2.5.1 Bulk density test
Take a specified volume in a glass cylinder (10 mL) with a
powder MNAC smaller than 100 μm and dried in an oven at
80 °C overnight. The cylinder was tapped for 1–2 min to
compact the carbon. The bulk density was measured (g/mL)
following Eq. (3) [80]:
 Biomass Conv. Bioref.

90
Weight of dry material ðgÞ
Bulk density ¼ 80
Volumeof packed dry material ðmlÞ

Removal % of iodine
70
 100 ð3Þ 60
The bulk density, moisture %, and ash content % of raw 50
material orange peel and MNAC samples are summarized in 40
Table 1. 30
20
2.5.2 Iodine number
10
The iodine number is known as the milligrams of iodine 0
adsorbed by 1.0 g of carbon that measure the micropore con- 0 50 100 150 200 250 300
tent of activated carbon. Different powdered MNAC samples Carbon dosage (mg)
(50–250 mg) were taken in a 250-mL flask and 10 mL of 5% Fig. 1 Iodine number removal % using MNAC samples (50–250 mg) at
HCl was added and the flask was stirred until the carbon room temperature
become wet. Then add 100 mL of the previously prepared
iodine solution from iodine (2.7 g) and potassium iodide dye adsorbed on 0.1 g of adsorbent) is used for mesoporosity
(4.1 g) in double distilled water (1 L) and shake the mixture measurement present in activated carbon [69]. The maximum
for 5 min. Then filtered off and 50 mL of filtrate was titrated MBN is 183.80 mg/g (Fig. 2).
against sodium thiosulfate (0.1 M) until the formation of pale
yellow solution followed by addition of starch indicator solu-
tion (1 mL of 1% concentration) and the titration was contin- 2.5.4 Determination of zero point of charge pHZPC
ued against sodium thiosulfate until the solution become col-
orless. A blank was similarly prepared without adding MNAC To determine the pHZPC value, 0.1 g of MNAC was intro-
sample (Fig. 1). The percentage of iodine removed was calcu- duced into 50 mL of 0.1 M NaNO3 solution with initial pH
lated by applying the following Eq. (4) [80]. The maximum range of 3–10 and was shaken for 24 h. After that, the sample
removal % was 79.13% for 0.2 g/L of MNAC. was separated from solution and equilibrium pH values of the
solution were measured. The difference between initial and
mL of Na2 S2 O3 used ðblankÞ−mL of Na2 S2 O3 used ðsampleÞ
equilibrium pH was plotted against initial pH of the solution.
Iodine removal% ¼  100
mL of Na2 S2 O3 used ðblankÞ The point at which the graph crossed the x-axis noted as
ð4Þ pHZPC value [46, 62, 69]. The pHZPC value of MNAC was
found to be basic pH 7.93 (Fig. 3).

2.5.3 Methylene blue test (batch experiments)

A total of 100 mL of methylene blue (MB) solutions with 200 183.80

initial concentrations of 50–200 mg/L were placed in 180
Erlenmeyer flasks to which an equal amounts of 0.1 g of 160 143.39
MNAC were added and kept in a shaker incubator at 30 °C
140
for 24 h until reach equilibrium. The concentrations of MB in
qe (mg/g)

the supernatant solution before and after adsorption were de- 120 99.87
termined using a spectrophotometer at λmax 665 nm. The 100
methylene blue number (MBN, the maximum amount of 80
60 49.92

Table 1 Ash %, moisture %, and bulk density (g/mL) of orange peel 40

and MNAC samples. 20
Sample Ash % Moisture % Bulk density (g/mL) 0
50 100 150 200
Orange peel 3.94 12.62 0.703 MB inial conc. (mg/L)
MNAC 0.66 12.28 0.650 Fig. 2 Methylene blue number using (50–200 mg/L initial concentration
of MB and 1.0 g/L of MNAC) at room temperature
Biomass Conv. Bioref.
2.5.5 Physical characterization of MNAC
TGA of the raw precursor (orange peel) was carried out by a
thermogravimetric analyzer (SDT Q600 V20.5 Build 15),
where sample was taken in silica crucible and subjected to
pyrolysis under N2 flow (100 mL/min) from 50 to 900 °C with
heating rate of 20 °C/min.
The morphology of the surface and pore size distribution of
optimized sample were observed by a scanning electron mi-
croscope (Quanta 250 FEG). It can be seen from the micro-
graphs where the external surface of the chemically activated
carbon is full of cavities.
A JEOL 100CX II transmission electron microscope
(TEM) 100 kV was used for MNAC nano-size analysis.
Alcohol was used as solvent to spread the sample on the grid
for TEM analysis. The porous characteristics of MNAC was
determined from N2 gas adsorption isotherm data performed
at 77 k. Before BET surface analysis, MNAC sample was
degased for 3 h at 300 °C under N2 gas. Surface area of the
samples was determined by applying BET (Brunauer-
Emmett-Teller) (SBET), and the total pore volume (VT) was
determined by the volume of N2 adsorbed at high relative
pressure [94]. The micropore surface area and micropore vol-
ume (Vm) were determined by using BELL SORP MINI II,
Japan. The pore size distribution (PSD) was estimated by MP
(micropore) analysis method.
2.5.6 Functional group analysis
The Fourier transform infrared (FTIR) spectrometry was ap-
plied in the characterization of the surface functional groups of
the prepared MNAC. To obtain the observed absorption
Fig. 3 Zero point of charge (pHZPC) of MNAC (100 mg) with initial pH
range of 3–10
spectra, the activated carbon was grounded to a very fine
powder and then dried at 70 °C overnight. The surface func-
tional groups of the MNAC were estimated by a Bruker
VERTEX 70v FTIR spectrometer connected to Platinum
ATR V-100 model in the wave number range (400–4000
cm−1).
2.5.7 Particle size analysis
The particle size of the MNAC powder activated carbon sam-
ples was analyzed using Malvern instruments Ltd, Master
Seizer 3000 (UK). Samples were dispersed in water under
stirring using and effective magnetic stirrer (2900 RPM) and
ultrasonic effect before feeding into the instrument. Using
laser diffraction technology that relies on the principle that
particles passing through a laser beam will scatter light at an
angle directly related to its size [29, 64]).
3 Results and discussion
3.1 Materials characteristics
3.1.1 Thermogravimetric analysis
Figure 4 shows the TGA and DTG analysis of weight loss of
orange peel (Fig. 4a) and orange peel/ZnCl2 (Fig. 4b) under
flow of N2 gas (100 mL/min). Orange peel presents four con-
tinuous regions of weight loss from 40 to 150 °C (9.084%
loss) and from 170 to 440 °C (30.39% loss), from 450 to
740 °C (25.17% loss), and 750 to 900 °C (3.48% loss) with
28.13% residue remained at 900 °C (Fig. 4a). The orange peel
weight-loss processes occurring below 600 °C are associated
with dehydration and release of volatiles from the cellulosic
structure. The DTG thermograms in Fig. 4a reveal that orange
peel sample was decomposed in three strong stages at 100,
225, and 590 °C and two small stages at 400 and 890 °C (Fig.
4a). The thermal analysis of the orange peel/ZnCl2 presents
four region weight loss (Fig. 4b). The complex thermal re-
sponse of orange peel/ZnCl2 is consistent with results reported
for the ZnCl2 activation of other biomass materials. The first
weight-loss step from 40 to 150 °C (7.30% loss, Fig. 4b) is
due to the dehydration process of the sample, which is pro-
moted by ZnCl2 Lewis acid nature, and the volatilization of
volatile fractions of the orange peel. The other three consecu-
tive weight-loss steps from 150 to 400 °C (49.55%, Fig. 4b),
450 to 650 °C (12.82%, Fig. 4b), and 650 to 900 °C (10.85%,
Fig. 4b), with 16.50% residue, remained at 900 °C (Fig. 4b).
The weight-loss step from 150 to 400 °C (49.55%, Fig. 4b)
includes the volatilization of ZnCl2. The third weight-loss step
from 450 to 650 °C (12.82%, Fig. 4b) includes carbon mass
loss via active pyrolysis and aromatic condensation reactions.
The condensation reactions promoted by ZnCl2 reduce tar
 Biomass Conv. Bioref.

Fig. 4 TGA and DTA under N2

atmosphere (100 mL/min) (a)
orange peel and (b) orange
peel/ZnCl2

formation and carbon gasification, which results in higher
activated carbon yields than activation without ZnCl2. The
weight losses at temperatures less than 100 °C for orange peel
and orange peel + ZnCl2 are due to water evaporation. The
DTG thermograms of orange peel/ZnCl2 sample (Fig. 4b)
showed that it decomposed in six states; the corresponding
peak temperatures of those stages are 100, 210, 250, 350,
550, and 850 °C. The stages at 210, 250, and 350 °C are
mainly attributed to the vaporization of ZnCl2 within the sam-
ple, while the stage at 550 °C is attributed to the carbonization
of orange peel to the activated carbon [65, 77].
3.1.2 Morphology analysis (SEM and TEM analysis)
The orange peel raw materials, orange peel/ZnCl2, and the
prepared MNAC were examined by a scanning electron
Biomass Conv. Bioref.

microscope (SEM) to analyze their surface physical morphol- 21.89%, and Cl 24.43%), and MNAC analysis has the element
ogy (Fig. 5a–c). The SEM micrographs of the orange peel and consisting of C (91.33%), O (5.77%), and Cl (2.90%).
its derivatives in Fig. 5a–c showed the presence of pores of
different sizes and shapes. In MNAC, a well-developed po-
3.1.4 Fourier transform infrared spectroscopy
rous surface was observed at higher magnification (Fig. 5c).
From the microscopic images, it can be seen that the outer
The surface chemistry of raw material orange peel, orange
surface of the MNAC is filled with cavities and that the dark
peel/ZnCl2, and MNAC samples was analyzed by FTIR and
area is considered micropore. The spaces found in activated
represented in Fig. 7a–c. FTIR of the orange peel showed
carbons known as pores are caused by evaporation of ZnCl2
broad intense absorption peaks around 3297.80 cm−1 which
during carbonization process. These observed pores from
is indicative of the existence of bonded hydroxyl groups, and
SEM images have a diameter in the micrometer (μm) range.
the peak observed at 2696 cm−1 can be assigned to the C-H
These pores are considered as channels to the microporous
group (Fig. 7a). The peak observed at 1607.37 cm−1 is due to
network [47, 48].
the C=C stretching that can be attributed to the aromatic bond.
MNAC was characterized by a transmission electron mi-
The peaks around 1428 cm−1 are due to the symmetric bend-
croscope (TEM) to measure its particle size. Fifty milliliters of
ing of C-H asymmetric, and the peaks at 1240 cm−1 are due to
ethanol was used as a solvent to spread the sample (10 mg) on
the C-O asymmetric stretching of aromatic ethers, esters, and
the grid and the image was presented in Fig. 5d. The TEM
phenols. The peak around 1014 cm−1 is due to C-O-C glyco-
analysis proved that the MNAC particle size is ranged be-
side ring [44, 65]. FTIR of orange peel impregnated with zinc
tween 10.4 and 33.3 nm.
chloride showed intense absorption peaks around 3368 cm−1
which consider hydroxyl groups (Fig. 7b).
3.1.3 Energy dispersive X-ray EDAX analysis The peak at 1610 cm−1 refers to the C=C stretching vibra-
tion in the aromatic C-C bond. The increase in the intensity of
Chemical compositions of the samples were analyzed with the peak at 1610 cm−1 (Fig. 7b) over the intensity of the same
EDAX (Fig. 6a–c). This analysis was carried out for the raw peak in Fig. 7a of orange peel indicates that impregnation with
materials of orange peel, orange peel (C 51.63%, O 45.16%), zinc chloride leads to an increase in the aromatic properties.
and element in orange peel/ZnCl2 (C 34.29%, O 18.31%, Zn The peak at 1017 cm−1 refers to C-O-C glycoside ring (Fig.

Fig. 5 SEM image of (a) raw

material of orange peel, (b) raw
material of orange peel/ZnCl2,
and (c) MNAC. d TEM analysis
in ethanol of MNAC

Fig. 6 EDAX (a) raw material of orange peel, (b) EDAX raw of orange peel/ZnCl2, and (c) MNAC
7b), where the FTIR for MNAC from orange peel indicates
that the presence of broad peaks around 3200 cm−1 corre-
spond to O-H stretching vibrations (Fig. 7c) where the peak
intensity highly decreased due to the decreasing in the OH in
the final product (MNAC). The peak at 2850 cm−1 refers to
the symmetric and asymmetric C-H stretching vibration of
aliphatic. The peak at 2320 cm−1 corresponds to CO2 (carbon
dioxide). The peak observed at 1798 cm−1 refers to C=O
stretching vibration of carboxyl groups and may be assigned
to carboxylic acids or to their esters. The peak observed at
Biomass Conv. Bioref.
1548 cm−1 is C=C that can be attributed to the aromatic C-C
bond. The peak observed at 1135 cm−1 is due to C-O-C bond,
and the peak observed at 617 is due to C-C stretching bond.
3.1.5 Particle size analysis
The results of the particle size distribution analysis of the
MNAC obtained at 2900 RPM rotation speed under ultrasonic
are presented in Fig. 8. The MNAC analysis showed two
narrow particle size distribution peaks with span 6.906 (span
Biomass Conv. Bioref.

Fig. 7 FTIR analysis of (a) raw a b

material of orange peel, (b) raw 100% 100%
material of orange peel/ZnCl2, 98%
95%
and (c) MNAC sample 96%

Transmiance [%]
Transmiance [%]
94% 90%
92% 85%
90%
88% 80%

86% 75%
84%
70%
82% Orange peel Orange peel/ZnCl2
80% 65%
3400 2400 1400 400 3400 2400 1400 400
Wavenumber cm–1 Wavenumber cm–1
c d
100% 100%
100%
95%
100%

Transmiance [%}
90%
Transmiance [%}

99%
99% 85%

99% 80%
99%
75%
99% MNAC
70% Orange peel
98% MNAC
Orange peel/ZnCl2
98% 65%
3400 2400 1400 400 3400 2400 1400 400
Wavenumber cm–1 Wavenumber cm–1

is the width of distribution, the narrower the distribution, the
smaller the span becomes). The particle size distribution anal-
ysis showed that about 10% of the MNAC represented a par-
ticle size below 35 nm. However, 50% of the sample reported
particle size less than 70.9 μm, and the rest of the sample has
particle size less than 490 μm.
3.1.6 Surface area, pore distribution, and porosity
N2 adsorption isotherm was carried out to study physical prop-
erty of activated carbon at 77 K, where nitrogen adsorption-
desorption curve provides qualitative information on the ad-
sorption mechanism and porous structure of the materials
(Fig. 9a). Adsorption-desorption analysis of MNAC sample
4.0
3.5
3.0
Volume Density (%)
exhibited adsorption isotherm curve type I as classified by
International Union of Pure and Applied Chemistry
(IUPAC) [79]. The adsorption isotherm implies that the acti-
vated carbons prepared by impregnation with zinc chloride are
micropore (mean pore diameter less than 2 nm). The results
agree with the porosity analysis obtained from t-plot which
had higher porosity 99.32%. The BET (Fig. 9b), MP (Fig. 9c),
and t-plot (Fig. 9d) surface area analyses obtained for the
MNAC sample are 1228.2, 1356.4, and 1492.8 m2/g [8].
The chemical activation of orange peel by ZnCl2 led to devel-
opment of activated carbon (MNAC) with high surface area
and micropore. Total pore volume of MNAC was calculated
to be 0.5482 cm3/g on the assumption of the cylindrical shape
of the micropore, and the pore diameter was calculated from
the BET analysis to be 0.7 nm, while the mean pore diameter
was 1.7965 nm [15].
3.2 Batch studies

2.5
2.0 3.2.1 Effect of pH on Cr(VI) adsorption
1.5
1.0 Solution pH is one of the important process parameters that
0.5 significantly influence the adsorption of Cr(VI) on adsorbent
0.0
[75, 89]. MNAC was employed for Cr(VI) ions removal at
0.0 0.1 1.0 10.0 100.0 1000.0 10000.0 different pH values (1.0–6.0). The preliminary experiments
Size classes (μm) were performed at definite experimental conditions (initial
Fig. 8 Particle size for MNAC using wet analysis in water at room chromium concentration 200 mg/L, adsorbent dose 1.0 g/L,
temperature. and 50-min contact time at room temperature). Figure 10
 Biomass Conv. Bioref.

Fig. 9 a Adsorption desorption

analysis of MNAC, b BET
surface area of MNAC, c MP
surface area curves of MNAC,
and d surface area curves from t-
plot of MNAC

shows the higher removal of Cr(VI) ions occurred at acidic pH
value. It is evident from pH study curve that the adsorption is
high at acidic pH (1.0–2.0), since it was about 62.56%. The
intensity of the metal adsorption can depend on the pH of the
solution largely due to the type and ionic state of the function-
al groups present on the adsorbent surface as well as on the
chemistry of the metals in the solution [18, 19]. High adsorp-
tion of Cr(VI) ions at a low pH may be an expected result due
to the availability of Cr(VI) ions in different shapes and sizes
in the acidic medium, and this may suit the nature of the
adsorbed surface in the acidic solution. At acidic pH, the pre-
dominant Cr(VI) ion species are HCrO4– and Cr2O72–, and
above neutral pH, only CrO 42– is stable. Under acidic
conditions, the adsorbent surface becomes very saturated with
protons and favors the adsorption of Cr(VI) ions in the anionic
form. As the pH of the solution increases, the degree of proton
on the surface gradually decreases resulting in decreased ab-
sorption of Cr(VI) ions. Moreover, as pH increases, there is a
competition between OH– and CrO42– ions, the former being
the dominant species at basic pH value. The decrease in net
positive surface charges on the adsorbent surface weakens the
electrostatic forces between the Cr(VI) ions and adsorbents,
eventually leading to a decrease in the adsorption capacity [18,
19]. Adsorption trends of Cr(VI) ions on MNAC attained
equilibrium at about 95 min. The Cr(VI) ions adsorption on

Fig. 10 Effect of pH on Cr(VI) 65 80

removal by MNAC (initial Cr(VI) 70
60
concentration 200 mg/L, MNAC
60
dose 1.0 g/L, contact time 55
Adsorpon%

100 min at room temperature)

Removal%

50
50
40
PH-1
45
30 PH-2.02
40 PH-3
20 pH-4
35 10 PH-5

30 0
0 2 4 6 8 0 30 60 90 120
pH Time(min)
Biomass Conv. Bioref.

MNAC was decreased from 69.25 to 48.98% with increase of
pH value from 2.0 to 6.0 (Fig. 10).
3.2.2 Effect of MNAC dose, initial Cr(VI) concentration,
and contact time
The effect of MNAC dose, initial Cr(VI) concentration, and
contact time on adsorption of Cr(VI) ions using MNAC is
illustrated in Fig. 11a–d. The maximum percentage of remov-
al of Cr(VI) ions was achieved using 3.0 g/L of MNAC dose
within 180 min (Fig. 11a). The higher initial concentration of
Cr(VI) ions provides good driving force to overcome mass
transfer resistances found between metal ions in the aqueous
solution and MNAC solid phase. A gradual increase in Cr(VI)
ions adsorption is observed for all experiments at different
concentrations with increasing dose of MNAC (Fig. 11 b, c).
The initial concentration of Cr(VI) ions in the solution is a
remarkable parameter as Cr(VI) ions concentration changes
over a broad range in industrial effluents. Figure 11c depicts
the changes in adsorption trends of MNAC with variation in
initial concentration of Cr(VI) ions in the solution. The ad-
sorption behavior in Fig. 11d clearly indicates the decreasing
trend of removal % from 99.24 to 42.97% as the initial Cr(VI)
ions concentration increased from 200 to 600 mg/L with con-
stant MNAC dosage (3 g/L) [33]. Figure 11a–d proves that the
nature of MNAC and the adsorption sites available on it high-
ly affected the rate of Cr(VI) ions removal. The Cr(VI) ions
absorption mechanism involves the transfer from solution to
the solid surface of MNAC by diffusion through the liquid
membrane around the adsorbed particles and diffusion
through the pores to the internal adsorption sites. The differ-
ence in concentration between the solution and the pores
available on the adsorbent surface is very large in the initial
stage, so the rate of adsorption of Cr(VI) ions is faster at the
beginning. This rate decreases in the later stage primarily due
to the slow pore diffusion of the solute into the bulk of the
adsorbent. For MANC, much difference in rate of adsorption
was observed within first 15 min and gradually reached its
maximum (99.47 %) within 3 h.
3.2.3 Effect of temperature
Effect of temperature (20–60 °C) on Cr(VI) ions (500 mg/L)
adsorption on MNAC (3.0 g/L) is presented in Fig. 12.
Removal % and adsorption capacity (Qe) of Cr(VI) ions onto
MNAC increased with increase in temperature from 20 to 60
°C (Fig. 12a, b), which indicates an endothermic adsorption
process. Since diffusion is an endothermic process, the diffu-
sion rate of solute into the pores of the adsorbent increases at
higher temperatures. Thus, the removal % of Cr(VI) ions in-
creases as the rate of diffusion of Cr(VI) ions in the external
mass transport process increases with temperature [58].
Increased adsorption with temperature is due to the endother-
mic nature of this adsorption and may also be attributed to the
increase in the adsorption sites number, which may be pro-
duced as a result of breaking the internal bonds near the sur-
face of adsorbent [58].

Fig. 11 a Effect of MNAC dose 100 120

(a) (b)
on Cr(VI) removal. b Relation 90
100
between MNAC dose and 80
removal with time (pH 1, Cr(VI) 70
Removal %

80
Removal %

concentration 300 mg/L, contact 60

time 3 h, at room temperature). c 50 60
Effect of initial concentration of 40 1.0 g/L
Cr(VI) ions on the removal % (pH 30
40 1.5 g/L
1, Cr(VI) ions concentration, 2.0g/L
20 2.5 g/L
20
200–600 mg/L). d Effect of 10 3.0 g/L
Cr(VI) initial concentration and 0 0
MNAC dose on removal % with 0 1 2 3 4 0 50 100 150 200
time (pH 1, MNAC dose 1.0–3.0 MNAC dosage (g/L) Time (min)
g/L)
100
100
(c) (d)
90
80 80
Removal %

70
Removal %

60 60
50
40 40
30 200 mg/L
200 mg/L 300 mg/L 300 mg/L
20 20
400 mg/L 500 mg/L 400 mg/L
10 600 mg/L 500mg/L
0 0
1.0 1.5 2.0 2.5 3.0 0 20 40 60 80 100 120 140 160 180
Carbon dose (g/L) Time (min)
 Biomass Conv. Bioref.

Fig. 12 Effect of temperature on

Cr(VI) ions adsorption by
MNAC. a Removal % versus
temperature. b Adsorption
capacity at equilibrium versus
temperature. c Removal % versus
time at different temperatures (pH
1.0, Cr(VI) concentration 500 mg/
L, MNAC dose 3.0 g/L, and
contact time 3.0 h)

3.2.4 Adsorption thermodynamic study adsorption of Cr(VI) ions. With increasing temperature,
ΔG° becomes more negative which demonstrate the increase
The nature of the adsorption of Cr(VI) on MNAC was pre- in the adsorption capability of Cr(VI) ions at a higher temper-
dicted by estimating the thermodynamic parameters such as ature and feasibility and thermodynamically spontaneous of
free energy (ΔG°), enthalpy (ΔH°), and entropy (ΔS°) using the adsorption process [53]. The positive values of ΔHo con-
the following Eq. (5) [17]. firmed the endothermic nature of the adsorbents for Cr(VI)
ions adsorption in the studied temperature range (30–60 °C).
ΔGo ¼ −RT lnK C ð5Þ
The positive values of ΔSo confirmed the randomness of the
where KC is the equilibrium constant and calculated as in adsorption process. Based on the value of the standard entropy
Eq. (6): which was higher than − 10 kJ/mol, it may be concluded that
in removal of Cr(VI) ions, dissociative mechanism is included
qe for MNAC [70, 92].
KC ¼ ð6Þ
Ce

The KC values were used to determine the ΔGo, ΔHo, and

3.2.5 Kinetics studies
ΔS from Eq. (7). The KC expressed in terms of the ΔHo (kJ/
o

mol) and ΔSo (kJ/mol) as a function of temperature:

The kinetic study of adsorption is a vital study for determining
ΔH °
ΔS ° the adsorption efficiency. Kinetic models are used to examine
lnK c ¼ þ ð7Þ the adsorption experiment data and to determine the adsorp-
RT R
tion mechanism and the potential rate control step that in-
ΔHo and ΔSo were obtained from the slopes and intercepts cludes mass transfer and the chemical process. These models
of the plots of ln Kc against 1/T (Fig. 13) ([68](. The free
energy change (ΔGo) indicates the degree of spontaneity of
the adsorption process, and also the higher negative value Table 2 Thermodynamic parameters
reflects a more energetically favorable adsorption (Table 2). ΔG° ΔH° (kJ/mol) ΔS° (kJ/mol)
The increase in negative value of ΔGo with increase of tem-
perature showed that the adsorption of Cr(VI) ions on MNAC 30 °C 40 °C 50 °C 60 °C
samples increased with increase in temperature, suggesting
− 145.19 − 1699 − 3543 − 5387 56,017.2 184.4
the higher number of active sites available for spontaneous
Biomass Conv. Bioref.

2.5
qt ¼ K dif t 1=2 þ C ð10Þ
2

1.5 The value of Kdif (mg/g min1/2) was determined from the
slope of respective plot of q versus t1/2 (Fig. 14c). If the ex-
1 periment is a batch system with rapid stirring and intraparticle
ln Kc

diffusion is the rate control step, then plot of qt versus t1/2 (Fig.
0.5
14c) will result in a linear relationship that passes through the
0 origin [14, 25]. The shape of Fig. 14c confirms that the lines
do not pass through the origin point and have correlation co-
-0.5 efficients ranging from low to high value without a specific
meaning (Table 4), which indicates that intraparticle diffusion
-1
2.9 3.0 3.1 3.2 3.3 3.4 3.5 is not the step to control the rate of absorption of Cr(VI) ions
on the MNAC but the other processes control the rate of
1/T × 10–3 (1/K)
adsorption.
–3
Fig. 13 Plot of ln Kc versus 1/T × 10 for adsorption of Cr(VI) ions (500 When the transfer of dissolved particles from the liquid
mg/L) on MNAC (3.0 g/L).
phase to the boundaries of the solid phase plays an important
role in adsorption, the liquid film diffusion model can be ap-
plied by Eq. (11) [10, 25]:
include pseudo-first- and second-order models, particle diffu-
sion, and film diffusion models [38]. lnð1− F Þ ¼ −K FD ðt Þ ð11Þ
Lagergren proposed a pseudo-first-order kinetic model that
was successfully applied to explain the kinetics of many ad- In order to assess the nature of the diffusion process respon-
sorption systems and the integral form of the pseudo-first- sible for adsorption of Cr(VI) ions on MNAC, –ln(1 – F) was
order model expressed as Eq. (8): plotted against time (t) (Fig. 14d), which gave a straight lines
that did not pass through the origin point [10, 25]. This indi-
k1 cates that film diffusion is not limiting step of the overall
logðqe −qt Þ ¼ logðqe Þ− t ð8Þ
2:303 adsorption process (Table 4).
The values of k1 and qe were measured from the slopes and
intercepts of log (qe–qt) against the t-plots (Fig. 14a), and the
3.2.6 Adsorption isotherm study
results are summarized in Table 3. The low correlation coef-
ficients (R2) obtained suggests that the adsorption of Cr(VI)
Adsorption isotherm demonstrates the interaction between ad-
ions on MNAC does not follow the Lagergren kinetic model
sorbate and adsorbent and is critical for design of adsorption
[9, 27].
process. The Langmuir and Freundlich isotherm models were
The adsorption kinetics additionally described by a
applied to investigate the adsorption process of Cr(VI) ions by
pseudo-second-order kinetic model that is represented in Eq.
MNAC at different conditions.
(9) [25, 39]:
The Langmuir isotherm is applicable to homogeneous
 
t 1 1 sorption on a surface that has equal sorption activation energy
¼ þ ðt Þ ð9Þ [13, 26, 51]. The Langmuir model assumes sorption occurred
qt k 2 q2e qe
on a surface containing a specified number of identical sites
The initial adsorption rate, h = (k2qe2), has been widely and only monolayer absorption occurred and no transmigra-
used for evaluation of the adsorption rates [42]. The pseudo- tion of adsorbate within the surface plane [16]. Therefore, the
second-order rate constants qe and k2 were calculated from the Langmuir isothermal model was chosen to estimate the max-
slopes and intercepts of the linear plots obtained by plotting t/ imum adsorption capacity resulting from full mono-coverage
qt versus t (Fig. 14b) and reported in Table 3. The results on the surface of the sorbent material. The Langmuir isotherm
showed correlation coefficient very close or equal to unity that model can be presented by linear Eq. (12):
explained a very good compliance with the pseudo-second-
Ce 1 1
order equation and the adsorption of Cr(VI) ions by MNAC ¼ þ  Ce ð12Þ
qe K L Qm Qm
followed pseudo-second-order kinetics.
Weber and Morris model is a widely used intraparticle where Qm consider a constant that show an entire mono-
diffusion model to predict the rate controlling step [25, 87, layer, and KL is adsorption equilibrium constant (L/mg) that is
88]. According to intraparticle diffusion model, the initial rate associated with the apparent energy of sorption [55]. The plots
of diffusion is given by Eq. (10): of Ce/qe versus Ce are linear which indicate that the adsorption
 Biomass Conv. Bioref.

Table 3 Pseudo-first- and second-order parameters for the adsorption of Cr(VI) ions on MNAC

First-order kinetic model Second-order kinetic model

Carbon conc. Cr+6 (mg L–1) qe (exp.) k1 × 103 qe (calc.) R2 k2 × 103 qe (calc.) h R2

1.0 g/L 200 141.353 26.950 44.470 0.9290 1.341 144.928 28.249 0.9972
300 208.120 8.520 49.660 0.7970 1.288 192.308 47.619 0.9984
400 131.130 13.130 140.280 0.8960 0.058 178.571 2.060 0.9557
500 126.700 13.130 99.930 0.9066 0.109 158.730 2.566 0.9821
600 147.170 8.520 70.960 0.7053 0.230 153.846 5.513 0.9434
1.5 g/L 200 180.100 21.190 44.340 0.9830 1.030 185.190 35.211 0.9995
300 140.850 10.820 23.340 0.9490 1.260 142.860 25.641 0.9989
400 124.400 7.600 101.438 0.9450 0.180 114.940 2.388 0.9877
500 87.860 13.130 45.092 0.9450 0.470 94.340 3.708 0.9955
600 127.550 10.130 75.440 0.9310 0.260 133.330 4.198 0.9796
2.0 g/L 200 96.990 22.340 33.744 0.9750 1.410 100.000 14.100 0.9994
300 124.590 9.210 22.248 0.8710 1.210 125.000 18.906 0.9982
400 119.060 9.210 61.958 0.9160 0.230 131.580 3.982 0.9835
500 105.940 17.040 76.643 0.9820 0.290 119.050 4.110 0.9964
600 98.770 8.750 43.391 0.9340 0.450 102.040 4.685 0.9888
2.5 g/L 200 79.308 38.00 31.886 0.9200 3.038 81.301 20.080 0.9999
300 113.590 17.500 41.172 0.9650 0.830 117.647 11.481 0.9983
400 110.755 10.820 57.056 0.9510 0.365 116.280 4.938 0.9948
500 123.925 14.050 81.771 0.9710 0.220 138.890 4.244 0.9935
600 113.094 11.280 63.023 0.9280 0.480 111.110 5.926 0.9925
3.0 g/L 200 66.316 43.760 11.298 0.9700 0.522 67.114 2.351 1.0000
300 99.123 21.420 26.491 0.9300 0.512 102.041 5.332 0.9998
400 122.956 12.440 73.249 0.9680 1.014 129.870 17.102 0.9980
500 117.610 12.670 66.742 0.9780 0.350 123.460 7.899 0.9946
600 106.604 7.830 49.442 0.9380 0.490 104.140 2.548 0.9974

data fitted reasonably to the Langmuir isotherm model (Fig.
15a). The constants were evaluated from the slope 1/Qm and
intercept 1/KaQm, where 1/Qm gives the theoretical monolayer
saturation capacity Q0 (Table 5).
The most important multisite or multilayer adsorption iso-
therm for heterogeneous surfaces is the Freundlich isotherm,
which is characterized by the heterogeneity factor 1/n, and is
represented by linear Eq. (13):
1 studies showed that Langmuir isotherm model is more applicable
log qe ¼ logK F þ logC e ð13Þ
n
If the values of n in the range 2–10, the adsorption will be
good, 1–2 the adsorption will be moderately good, and less
than 1 the adsorption will be poor. The intercept log KF is a
measure of adsorption capacity, and the slope 1/n is the
adsorption intensity (Table 5). To determine the maximum
adsorption capacity, it is needful to operate with constant
initial concentration C0 and variable weights of adsorbent
thus in QmF is the extrapolated value of log qe for C = C0.
According to Halsey, Eq. (14) [35]:
1=n
QmF ¼ K F C 0 ð14Þ
The values of KF and n were calculated from the intercept
and slope of the plots Log qe against Log Ce (Fig. 15b). The
Freundlich isotherm was found to be linear with correlation coef-
ficients ranged between 0.830 and 0.9997 (Table 5). The isotherm
to the adsorption data than Freundlich isotherm model suggesting
a homogeneous nature of MNAC sample. The maximum adsorp-
tion capacity by Freundlich isotherm models (QmF) is very near
from that obtained from Langmuir isotherm model (Qm).
3.2.7 Regeneration of AC prepared from orange peel
Adsorption by activated carbons is vastly used technology for
removing of pollutants from wastewater, and the economy of
Biomass Conv. Bioref.

Fig. 14 Kinetic adsorption 3.0 200 mg/L 300 mg/L 400 mg/L
2.5 200 mg/L 300 mg/L 400 mg/L
models of Cr(VI) ions on MNAC 2.0
500 mg/L 600 mg/L 500 mg/L 600 mg/L
2.5
(3.0 g/L). a Pseudo-first-order
1.5
plots. b Pseudo-second-order

t/qt(min g/mg)
2.0
plots. c Intraparticle diffusion 1.0

Log(qe-qt)
model. d Film diffusion model 0.5 1.5
0.0
-0.5 1.0

-1.0
0.5
-1.5 (a) (b)
-2.0 0.0
0 100 200 300 0 100 200 300
Time (min) Time (min)

250 6.0 200 mg/L

(c) (d)
300 mg/L
5.0 400 mg/L
200 500 mg/L
4.0 600 mg/L
qt (mg/g)

150

-ln(1-F)
3.0
100 200 mg/L
300 mg/L 2.0
400 mg/L
50
500 mg/L 1.0
600 mg/L
0 0.0
0 5 10 15 20 0 100 200 300
Time1/2 (min.) Time (min)

this technology extremely depends on the reuse of activated utilized for the regeneration of exhausted MNAC. The
carbons. Several regeneration techniques for activated carbons MNAC was regenerated by washing with 0.1 N NaOH solu-
such as chemical, thermal, and wet air oxidation regenerations tion, 0.1 M HCl, and then followed by hot distilled water [41].
are well confirmed. Chemical regeneration technique is The maximum removal of Cr(VI) ions by MNAC was found

Table 4 Intraparticle diffusion

and film diffusion model MNAC dose (g/L) Cr(VI) (mg L–1) Intraparticle diffusion Film diffusion
parameter for adsorption of
Cr(VI) ions on MNAC Kdif C R2 KFD C R2

1.0 200 3.6075 102.260 0.9621 0.0256 1.208 0.929

300 4.0710 148.620 0.9536 0.0085 1.433 0.797
400 8.2159 5.6435 0.9889 0.0129 − 0.055 0.928
500 6.5138 31.8430 0.9729 0.0123 0.370 0.888
600 5.3769 62.6130 0.8630 0.0098 0.579 0.644
1.5 200 3.373 139.070 0.947 0.0212 1.402 0.983
300 2.045 112.490 0.938 0.0108 1.839 0.895
400 7.583 1.6270 0.961 0.0077 0.2068 0.956
500 3.696 35.347 0.960 0.0131 0.666 0.945
600 5.027 48.305 0.972 0.0101 0.525 0.931
2.0 200 0.128 78.798 0.893 0.0213 1.109 0.977
300 1.178 104.130 0.962 0.0091 1.724 0.872
400 5.239 41.847 0.962 0.0093 0.652 0.916
500 4.905 37.652 0.960 0.0170 0.319 0.982
600 3.111 49.146 0.963 0.0077 0.891 0.963
2.5 200 1.583 61.728 0.910 0.0339 1.135 0.949
300 2.610 78.114 0.970 0.0174 1.014 0.966
400 4.807 40.526 0.943 0.0109 0.664 0.951
500 6.150 37.355 0.960 0.0140 0.407 0.971
600 4.051 50.434 0.964 0.0124 0.534 0.939
3.0 200 0.434 61.796 0.818 0.0422 1.842 0.960
300 1.838 75.736 0.876 0.0243 1.185 0.993
400 5.316 45.062 0.942 0.0124 0.518 0.968
500 4.519 50.634 0.965 0.0126 0.566 0.978
600 3.720 45.306 0.945 0.0077 0.769 0.938
 Biomass Conv. Bioref.

Table 5 The Langmuir and

Freundlich isotherm model Isotherm model Parameters MNAC dose
parameters for adsorption of
Cr(VI) ions on MNAC 1.0 g/L 1.5 g/L 2.0 g/L 2.5 g/L 3.0 g/L

Langmuir Qm (mg/g) 133.33 102.04 99.01 114.94 107.53

KL × 103 − 97.40 − 53.85 − 88.83 − 1740.00 − 39.57
R2 0.978 0.913 0.995 0.9965 0.9975
Freundlich 1/n − 0.0561 1.5451 1.8806 0.0784 − 0.026
KF 177.87 0.03 0.01 76.42 124.45
QmF (mg/g) 132.13 201.61 108.33 124.40 105.38
R2 0.979 0.967 0.9997 0.923 0.830

Fig. 15 a Langmuir isotherm 4.5 (a) 3.0 (b)

model plot. b Freundlich isotherm 4.0
2.5
model plot of adsorption of 3.5
Cr(VI) ions onto MNAC at room 3.0 2.0
temperature

Log qe
2.5
Ce/qe

1.0 g/L 1.5 1.0 g/L

2.0
1.5 g/L 1.5 g/L
1.5 2.0 g/L 1.0 2.0 g/L
1.0 2.5 g/L 2.5 g/L
3.0 g/L 0.5 3.0 g/L
0.5
0.0 0.0
0 100 200 300 400 500 0.0 0.5 1.0 1.5 2.0 2.5 3.0
Ce (mg/L) Log Ce

to be 99.12, 77.99, 75.39, 74.03, and 73.18% for the 1st, 2nd,
3rd, 4th, and 5th regeneration cycles, respectively (Fig. 16),
which proved the regeneration possibility of MNAC. The de-
crease in adsorption occurs with an obvious increase in the
number of cycles, which occurred mainly after the first cycle.
This is due to the fact that the regeneration efficiency after the
first cycle is not very effective and it showed incomplete re-
moval of the adsorbed chromium (VI) by MNAC, or this may
100
90
80
70
Removal %
be due to the presence of clogging in some of the MNAC
pores, which reduces the adsorption in the following cycles.
4 Conclusion
This work reported a fabrication of a novel microporous nano-
activated carbons (MNAC) with high-specific surface area
(1228.2 m2/g) type-I from orange peel/ZnCl2 at 700 °C to be
used as adsorbent materials for adsorption of Cr(VI) ions from
aqueous environment. Fabricated MNAC was identified as an
efficient adsorbent for the elimination of hexavalent chromi-
um from aqueous solution. The developed MNAC showed
high adsorption capacity for both MB and iodine. The
MNAC pHpzc value was found to be 7.6. The adsorption pro-

60 cess was found to influence by different parameters such as

50 1st Cycle (99.12%) adsorbent dose, pH, initial Cr(VI) ions concentrations, and
40 2nd Cycle (77.99) contact time. The best fit of the experimental result was ob-
30 3rd Cycle (75.39%) tained with Langmuir isotherm model. The adsorption process
20 4rd Cycle (74.03%) could be better described by the pseudo-second-order model.
10 5rd Cycle (73.18%) Results of thermodynamic experiments showed that adsorp-
0 tion of Cr(VI) ions increased with increasing of the tempera-
0 100 200 300 ture. Results of determination of the thermodynamic parame-
Time (min) ters indicated that adsorption process is spontaneous in nature,
Fig. 16 Removal % of Cr(VI) ions (300 mg/L) by MNAC (3 g/L) at room endothermic, and also, increasing of the temperature favor the
temperature for five cycles adsorption of Cr(VI) ions onto MNAC. The maximum
Biomass Conv. Bioref.
adsorption capacity of Cr(VI) ions by MNAC was 133.33 mg/
g. The removal % of Cr(VI) ions on MNAC decreased from
99.12 to 73.18% after five cycles; therefore, MNAC can still
be considered as an adsorbent with potential for the removal
of Cr(VI) ions from wastewater.
References
1. Abdelwahab O, El Sikaily A, Khaled A, El Nemr A (2007) Mass
transfer processes of Chromium (VI) adsorption onto Guava seeds.
Chem Ecol 23(1):73–85
2. Abdullah N, Yusof N, Lau WJ, Jaafar J, Ismail AF (2019) Recent
trends of heavy metal removal from water/wastewater by mem-
brane technologies. J Ind Eng Chem 76:17–38. https://doi.org/10.
1016/j.jiec.2019.03.029
3. Abdullah WNAS, Tiandee S, Lau W-J, Aziz F, Ismail AF (2020)
Potential use of nanofiltration like-forward osmosis membranes for
copper ion removal. Chin J Chem Eng 28(2):420–428. https://doi.
org/10.1016/j.cjche.2019.05.016
4. Alghamdi MM, El-Zahhar AA, Idris AM, Sadi TO, Sahlabji T, El
Nemr A (2019) Synthesis, characterization and application of a new
polymeric-clay-magnetite composite resin for water softening. Sep
Purif Technol 224:356–365. https://doi.org/10.1016/j.seppur.2019.
05.037
5. Ali H, Khan E, Ilahi I (2019) Environmental chemistry and ecotox-
icology of hazardous heavy metals: environmental persistence, tox-
icity, and bioaccumulation. J Chem 6730305. https://doi.org/10.
1155/2019/6730305
6. Araucz K, Aurich A, Kołodyńska D (2020) Novel multifunctional
ion exchangers for metal ions removal in the presence of citric acid.
Chemosphere 251:126331. https://doi.org/10.1016/j.chemosphere.
2020.126331
7. Bezzina JP, Robshaw T, Dawson R, Ogden MD (2020) Single
metal isotherm study of the ion exchange removal of Cu(II),
Fe(II), Pb(II) and Zn(II) from synthetic acetic acid leachate. Chem
Eng J 394:124862. https://doi.org/10.1016/j.cej.2020.124862
8. Boonpoke A, Chiarakorn S, Laosiripojana N, Towprayoon S,
Chidthaisong A (2011) Synthesis of activated carbon and MCM-
41 from bagasse and rice husk and their carbon dioxide adsorption
capacity. J Sust Energy Environ 2:77–81
9. Boudrahem F, Aissani-Benissad F, Aït-Amar H (2009) Batch sorp-
tion dynamics and equilibrium for the removal of lead ions from
aqueous phase using activated carbon developed from coffee resi-
due activated with zinc chloride. J Environ Manag 90:3031–3039
10. Boyd GE, AdamSon AM, Myers LS (1949) The exchange adsorp-
tion of ions from aqueous solution by organic zeolites. J Am Chem
Soc 69:2836
11. Bremner C, Cochrane TA, McGuigan P, Bello-Mendoza R (2020)
Removal of dissolved heavy metals from storm water by filtration
with granular recycled glass and mussel shell with and without
microalgae biofilm. Environ Technol Innov 18:100662. https://
doi.org/10.1016/j.eti.2020.100662
12. Chen Q, Yao Y, Li X, Lu J, Zhou J, Huang Z (2018) Comparison of
heavy metal removals from aqueous solutions by chemical precip-
itation and characteristics of precipitates. J Water Process Eng 26:
289–300. https://doi.org/10.1016/j.jwpe.2018.11.003
13. Choy KKH, Porter JF, McKay G (2000) Langmuir isotherm models
applied to the multicomponent sorption of acid dyes from effluent
onto activated carbon. Chem Eng J 45:575–584
14. Crini HN, Peindy F, Gimbert C (2007) Robert, Removal of C.I.
Basic Green 4 (Malachite Green) from aqueous solutions by
adsorption using cyclodextrin-based adsorbent: kinetic and equilib-
rium studies. Sep Purif Technol 53:97–110
15. Dobahi A, Shu Y, Hasegawa T, Maruyama J, Iwasaki S, Shen Y,
Uyama H (2015) Preparation of activated carbon by KOH activa-
tion from Amygdalus Pedunculata shell and its application for elec-
tric double-layer capacitor. J Electrochem 83(5):351–353
16. Doğan M, Alkan M, Organer Y (2000) Adsorption of methylene
from aqueous solution onto perlite. Water Air Soil Pollut 120:229–
249
17. Dwivedi CP, Sahu JN, Mohanty CR, Raj Mohan B, Maikap BC
(2008) Column performance of granular activated carbon packed
bed for Pb(II) removal. J Hazard Mater 156(1-3):596–603
18. El Nemr A (2007) Pomegranate husk as an adsorbent in the removal
of toxic chromium from wastewater. Chem Ecol 23(5):409–425.
https://doi.org/10.1080/02757540701653350
19. El Nemr A (2009) Potential of pomegranate husk carbon for Cr(VI)
removal from wastewater: kinetic and isotherm studies. J Hazard
Mater 161:132–141. https://doi.org/10.1016/j.jhazmat.2008.03.093
20. El Nemr A (ed) (2011) Impact, monitoring and management of
environmental pollution. Nova Science Publishers, Inc.
Hauppauge, New York. [ISBN-10: 1608764877, ISBN-13:
9781608764877], p 638
21. El Nemr A (ed) (2012) Non-Conventional textile waste water treat-
ment. Nova Science Publishers, Inc. Hauppauge, New York. [Hard
cover ISBN: 978-1-62100-079-2, e-book ISBN: 978-1-62100-228-
4], p 267
22. El Nemr A, El Sadaawy MM, Khaled A, El Sikaily A (2014)
Adsorption of the anionic dye Direct Red 23 onto new activated
carbons developed from Cynara cardunculus: kinetics, equilibrium
and thermodynamics. Blue Biotechnol J 3(1):121–142
23. El Nemr A, El Sikaily A, Khaled A, Abdelwahab O (2007)
Removal of toxic chromium (VI) from aqueous solution by activat-
ed carbon using Casuarina Equisetifolia. Chem Ecol 23(2):119–
129
24. El Nemr A, El Sikaily A, Khaled A, Abdelwahab O (2015)
Removal of toxic chromium from aqueous solution, wastewater
and saline water by marine red alga Pterocladia capillacea and
its activated carbon. Arab J Chem 8:105–117. https://doi.org/10.
1016/j.arabjc.2011.01.016
25. El Nemr A, El-Sikaily A, Khaled A (2010) Modeling of adsorption
isotherms of Methylene Blue onto rice husk activated carbon. Egypt
J Aquat Res 36(3):403–425
26. El Nemr A, Ismail MNM, El Ashry ESH, Abdel Hamid H (2020)
Novel simple modification of chitosan as adsorptive agent for re-
moval of Cr6+ from aqueous solution. Egypt J Chem 63(4):21–22.
https://doi.org/10.21608/ejchem.2019.11157.1716
27. El Nemr A, Khaled A, Abdelwahab O, El-Sikaily A (2008)
Treatment of wastewater containing toxic chromium using new
activated carbon developed from date palm seed. J Hazard Mater
152(1):263–275
28. El Nemr A, Ragab S (2018) Acetylation of Cotton-Giza 86 cellu-
lose using MnCl2 as a new catalyst and its application to machine
oil removal. Environ Process 5(4):895–905. https://doi.org/10.
1007/s40710-018-0330-7
29. El Nemr A, Ragab S, El Sikaily A (2017) Rapid synthesis of cel-
lulose triacetate from cotton cellulose and its effect on specific
surface area and particle size distribution. Iran Polym J 26(4):
261–272. https://doi.org/10.1007/s13726-017-0516-2
30. El Sikaily A, El Nemr A, Khaled A, Abdelwahab O (2007)
Removal of toxic chromium from wastewater using green alga
Ulva lactuca and its activated Carbon. J Hazard Mater 148:216–228
31. Eldeeb TM, El Nemr A, Khedr MH, El-Dek SI, Imam NG (2020)
Novel, three-dimensional, chitosan-carbon nanotube–PVA nano-
composite hydrogel for removal of Cr6+ from water. Desalin
Water Treat 184:163–177

32. Eleryan A, El Nemr A, Mashaly M, Khaled A (2019) 6-
T r i e t h y l e n e t e t r a m i n e 6 - d eo x y c e l l u l o s e gr a f t e d wi t h
crotonaldehyde as adsorbent for Cr6+ removal from wastewater.
Int J Sci Eng Res 10(7):1199–1211
33. Esmaeili A, Ghasemi S, Rustaiyan A (2010) Removal of hexavalent
chromium using activated carbons derived from marine algae
Gracilaria and Sargassum sp. J Mar Sci Technol 18(4):587–592
34. Fernandez ME, Nunell GV, Bonelli PR, Cukierman AL (2014)
Activated carbon developed from orange peels: batch and
dynamiccompetitive adsorption of basic dyes. Ind Crop Prod 62:
437–445. https://doi.org/10.1016/j.indcrop.2014.09.015
35. Halsey GD (1952) The role of surface heterogeneity. Adv Catal 4:
259–269
36. Hao J, Ji L, Li C, Hu C, Wu K (2018a) Rapid, efficient and eco-
nomic removal of organic dyes and heavy metals from wastewater
by zinc-induced in-situ reduction and precipitation of graphene ox-
ide. J Taiwan Inst Chem Eng 88:137–145. https://doi.org/10.1016/j.
jtice.2018.03.045
37. Hashemian S, Salari K, Yazdi ZA (2014) Preparation of activated
carbon from agricultural wastes (almond shell and orange peel) for
adsorption of 2-pic from aqueous solution. J Ind Eng Chem 20:
1892–1900. https://doi.org/10.1016/j.jiec.2013.09.009
38. Ho YS (2004) Citation review of Lagergren kinetic rate equation on
adsorption reactions. Scientometrics 59:171–177
39. Ho YS, McKay G (2000) The kinetics of biosorption of divalent
metal ions onto sphagnum moss peat. Water Res 34:735–742
40. Hosseini SM, Alibakhshi H, Jashni E, Parvizian F, Shen JN, Taheri
M, Ebrahimi M, Rafiei N (2020) A novel layer-by-layer heteroge-
neous cation exchange membrane for heavy metal ions removal
from water. J Hazard Mater 381:120884. https://doi.org/10.1016/j.
jhazmat.2019.120884
41. Hu Z, Lei L, Li Y, Ni Y (2003) Chromium adsorption on high-
performance activated carbons from aqueous solution. Sep Purif
Technol 31:13–18
42. Karthikeyan S, Balasubramanian R, Iyer CSP (2007) Evaluation of
the marine algae Ulvafasciata and Sargassumsp. For the
biosorption of Cu(II) from aqueous solutions. Bioresour Technol
98(2):452–455
43. Khaled A, El Nemr A, El-Sikaily A, Abdelwahab O (2009a)
Removal of Direct N Blue-106 from artificial textile dye effluent
using activated carbon from orange peel: adsorption isotherm and
kinetic studies. J Hazard Mater 165:100–110. https://doi.org/10.
1016/j.jhazmat.2008.09.122
44. Khaled A, El Nemr A, El-Sikaily A, Abdelwahab O (2009b)
Treatment of artificial textile dye effluent containing Direct
Yellow 12 by orange peel carbon. Desalination 238:210–232
45. King JF, Szczuka A, Zhang Z, Mitch WA (2020) Efficacy of ozone
for removal of pesticides, metals and indicator virus from reverse
osmosis concentrates generated during potable reuse of municipal
wastewaters. Water Res 176:115744. https://doi.org/10.1016/j.
watres.2020.115744
46. Kragović M, Stojmenović M, Petrović J, Loredo J, Pašalić S,
Nedeljković A, Ristović I (2019) Influence of alginate encapsula-
tion on point of zero charge (pHpzc) and thermodynamic properties
of the natural and Fe(III) - modified zeolite. Procedia Manuf 32:
286–293. https://doi.org/10.1016/j.promfg.2019.02.216
47. Kula I, Uğurlu M, Karaoğlu H, Celik A (2008a) Adsorption of
Cd(II) ions from aqueous solutions using activated carbon prepared
from olive stone by ZnCl2 activation. Bioresour Technol 99:492–
501
48. Kula I, Uğurlu M, Karaoğlu H, Celik A (2008b) Adsorption of
Cd(II) ions from aqueous solutions using activated carbon prepared
from olive stone by ZnCl2 activation. J. Bioresour Technol 99:492–
501
49. Kwon D, Oh J-I, Lam SS, Moon DH, Kwon EE (2019) Orange peel
valorization by pyrolysis under the carbon dioxide environment.
Biomass Conv. Bioref.
Bioresour Technol 285:121356. https://doi.org/10.1016/j.biortech.
2019.121356
50. Lam SS, Liew RK, Wong YM, Yek NYP, Ma NL, Lee CL, Chase
HA (2017) Microwave-assisted pyrolysis with chemical activation,
an innovative method to convert orange peel into activated carbon
with improved properties as dye adsorbent. J Clean Prod 162:1376–
1387. https://doi.org/10.1016/j.jclepro.2017.06.131
51. Langmuir I (1916) The constitution and fundamental properties of
solids and liquids. J Am Chem Soc 38:2221–2295
52. Li H, Yan Z, Li Y, Hong W (2020a) Latest development in salt
removal from solar-driven interfacial saline water evaporator: ad-
vanced designs and challenges. Water Res 177:115770. https://doi.
org/10.1016/j.watres.2020.115770
53. Li Y, Xia B, Zhao Q, Liu F, Du Q, Wang D, Li D, Wang Z, Zhang
P, Xia Y (2011) Removal of copper ions from aqueous solution by
calcium alginate immobilized kaolin. J Environ Sci 23:404–411
54. Li Y-L, Wang J, Yue Z-B, Tao W, Yang H-B, Zhou Y-F, Chen T-H
(2020b) Simultaneous chemical oxygen demand removal, methane
production and heavy metal precipitation in the biological treatment
of landfill leachate using acid mine drainage as sulfate resource. J
Biosci Bioeng 124(1):71–75. https://doi.org/10.1016/j.jbiosc.2017.
02.009
55. Longhinotti E, Poza F, Furlan L, Sanchez MDND, Klug M,
Laranjeira MCM, Favere TV (1998) Adsorption of anionic dyes
on the biopolymer chitin. J Braz Chem Soc 9:435–440
56. Lopez J, Reig M, Gibert O, Valderrama C, Cortina JL (2018)
Evaluation of NF membranes as treatment technology of acid mine
drainage: metals and sulfate removal. Desalination 440:122–134.
https://doi.org/10.1016/j.desal.2018.03.030
57. Manna MC, Sahu A, De N, Thakur JK, Mandal A, Bhattacharjya S,
Ghosh A, Rahman MM, Naidu R, Singh UB, Dakhli R, Sharma
MP, Misra S (2020) Novel bio-filtration method for the removal of
heavy metals from municipal solid waste. Environ Technol Innov
17:100619. https://doi.org/10.1016/j.eti.2020.100619
58. Meena AK, Mishra GK, Rai PK, Rajagopal C, Nagar PN (2008)
Removal of heavy metal ions from aqueous solutions using carbon
aerogel as an adsorbent. J Hazard Mater 150:604–611
59. Mehmood A, Raza W, Kim K-H, Raza N, Lee SS, Zhang M, Lee J-
H, Sarfraz M (2019) Spatial distribution of heavy metals in crops in
a wastewater irrigated zone and health risk assessment. Environ Res
168:382–388. https://doi.org/10.1016/j.envres.2018.09.020
60. Mobarak M, Mohamed EA, Selim AQ, Sellaoui L, Lamine AB,
Erto A, Bonilla-Petriciolet A, Seliem MK (2019) Surfactant–
modified serpentine for fluoride and Cr(VI) adsorption in single
and binary systems: experimental studies and theoretical modeling.
Chem Eng J 369:333–343. https://doi.org/10.1016/j.cej.2019.03.
086
61. Mohamed EA, Selim AQ, Ahmed SA, Sellaoui L, Bonilla-
Petriciolet A, Erto A, Li Z, Li Y, Seliem MK (2020) H2O2-activat-
ed anthracite impregnated with chitosan as a novel composite for
Cr(VI) and methyl orange adsorption in single-compound and bi-
nary systems: modeling and mechanism interpretation. Chem Eng J
380:122445. https://doi.org/10.1016/j.cej.2019.122445
62. Ozdemir I, Şahin M, Orhan R, Erdem M (2014) Preparation and
characterization of activated carbon from grape stalk by zinc chlo-
ride activation. Fuel Process Technol 125:200–206
63. Porter DJ, Raymond LW, Anastasio GD (1999) Chromium: friend
or foe. Arch Fam Med 8:386–390
64. Ragab S, El Nemr A (2018a) Nanofiber cellulose di- and tri-acetate
using ferric chloride as a catalyst promoting highly efficient synthe-
sis under microwave irradiation. J Macromol Sci A 55(2):124–134.
https://doi.org/10.1080/10601325.2017.1387741
65. Ragab S, El Nemr A (2019) Zirconyl chloride as a novel and effi-
cient green Lewis acid catalyst for direct acetylation of cotton cel-
lulose in the presence and absence of solvent. J Polym Res 26:156.
https://doi.org/10.1007/s10965-019-1816
Biomass Conv. Bioref.
66. Rai PK, Lee SS, Zhang M, Tsang YF, Kim K-H (2019) Heavy
metals in food crops: health risks, fate, mechanisms, and manage-
ment. Environ Int 125:365–385. https://doi.org/10.1016/j.envint.
2019.01.067
67. Rawat AP, Singh DP (2019) Synergistic action of adsorption and
reductive properties of ash derived from distilled Mentha piperita
plant waste in removal of Cr(VI) from aqueous solution. Ecotoxicol
Environ Saf 176:27–33
68. Romero-Gonzalez J, Peralta-Videa JR, Rodriguez E, Ramirez SLJL
(2005) Determination of thermodynamic parameters of Cr(VI) ad-
sorption from aqueous solution onto Agave lechuguilla biomass. J
Chem Thermodyn 37:343–347
69. Rostamian R, Heidarpour M, Mousavi FS, Afyuni M (2015)
Characterization and sodium sorption capacity of biochars and ac-
tivated carbon prepared from rice husk. J Agric Sci Technol 17:
1057–1069
70. Scheckel K, Sparks D (2001) Temperature effects on nickel sorp-
tion kinetics at the mineral water interface. Soil Sci Soc Am J 65:
719–728
71. Seliem MK, Mobarak M, Selim AQ, Mohamed EA, Halfaya RA,
Gomaa HK, Anastopoulos I, Giannakoudakis DA, Lima EC,
Bonilla-Petriciolet A, Dotto GL (2020) A novel multifunctional
adsorbent of pomegranate peel extract and activated anthracite for
Mn(VII) and Cr(VI) uptake from solutions: experiments and theo-
retical treatment. J Mol Liq 311:113169. https://doi.org/10.1016/j.
molliq.2020.113169
72. Selim AQ, Mohamed EA, Mobarak M, Zayed AM, Seliem MK,
Komarneni S (2018) Cr(VI) uptake by a composite of processed
diatomite with MCM-41: Isotherm, kinetic and thermodynamic
studies. Microporous Mesoporous Mater 260:84–92. https://doi.
org/10.1016/j.micromeso.2017.10.041
73. Serag E, El Nemr A, Abdel Hamid FF, Fathy SA, El-Maghraby A
(2018) A novel three dimensional carbon nanotube-polyethylene
glycol - polyvinyl alcohol nanocomposite for Cu(II) removal from
water. Egypt J Aquat Biol Fish 22(2):103–118
74. Serag E, El Nemr A, El-Maghraby A (2017) Synthesis of highly
effective novel graphene oxide-polyethylene glycol-polyvinyl alco-
hol nanocomposite hydrogel for copper removal. J Water Environ
Nanotechnol 2(4):223–234
75. Shi D, Cui B, Li L, Xu M, Zhang Y, Peng X, Zhang L, Song F, Ji L
(2020a) Removal of calcium and magnesium from lithium concen-
trated solution by solvent extraction method using D2EHPA.
Desalination 479:114306. https://doi.org/10.1016/j.desal.2019.
114306
76. Shi X, Qiao Y, An X, Tian Y, Zhou H (2020b) High-capacity
adsorption of Cr(VI) by lignin-based composite: characterization,
performance and mechanism. Int J Biol Macromol 159:839–849.
https://doi.org/10.1016/j.ijbiomac.2020.05.130
77. Shoaib AGM, El-Sikaily A, El Nemr A, Mohamed AE-DA, Hassan
AA (2020a) Preparation and characterization of highly surface area
activated carbons followed type IV from marine red alga
(Pterocladia capillacea) by zinc chloride activation. Biomass
Convers Biorefin. In press. https://doi.org/10.1007/s13399-020-
00760-8
78. Shoaib AGM, El-Sikaily A, El Nemr A, Mohamed AE-DA, Hassan
AA (2020b) Testing the carbonization condition for high surface
area preparation of activated carbon followed type IV from green
alga Ulva lactuca. Biomass Convers Biorefin In press 11(06):2020.
https://doi.org/10.1007/s13399-020-00823-w
79. Sing KSW, Everret DH, Haul RAW, Moscou L, Pierotti RA,
Rouquerol J, Siemieniewska T (1985) Reporting physisorption data
for gas/solid systems with special reference to the determination of
surface area and porosity. Pure Appl Chem 57:603–619
80. Sugumaran P, Priya Susan V, Ravichandran P, Seshadri S (2012)
Production and characterization of activated carbon from banana
empty fruit and Delonix regia fruit pod. J Sust Energy Environ 3:
125–132
81. Sun R, Li Y, Lin N, Ou C, Wang X, Zhang L, Jiang F (2020)
Removal of heavy metals using a novel sulfidogenic AMD treat-
ment system with sulfur reduction: configuration, performance,
critical parameters and economic analysis. Environ Int 136:
105457. https://doi.org/10.1016/j.envint.2019.105457
82. Sun R, Zhang L, Zhang Z, Chen G-H, Jiang F (2018) Realizing
high-rate sulfur reduction under sulfate-rich conditions in a biolog-
ical sulfide production system to treat metal-laden wastewater defi-
cient in organic matter. Water Res 131:239–245
83. Swaidan A, Borthakur P, Boruah PK, Das MR, Barras A, Hamieh
S, Boukherroub R (2019) A facile preparation of CuS-BSA nano-
composite as enzyme mimics: application for selective and sensi-
tive sensing of Cr(VI) ions. Sensors Actuators B Chem 294:253–
262
84. Tran T-K, Chiu K-F, Lin C-Y, Leu H-J (2017) Electrochemical
treatment of wastewater: selectivity of the heavy metals removal
process. Int J Hydrog Energy 42(45):27741–27748. https://doi.
org/10.1016/j.ijhydene.2017.05.156
85. Ververis C, Georghiou K, Danielidis D, Hatzinikolaou DG, Santas
P, Santas R, Corleti V (2007) Cellulose, hemicelluloses, lignin and
ash content of some organic materials and their suitability for use as
paper pulp supplements. J. Bioresour Technol 98:296–301
86. Volesky B (1990) Biosorption of metals. CRc press, Boston
87. Wang L, Zhang J, Zhao R, Li Y, Li C, Zhang C (2010) Adsorption
of Pb(II) on activated carbon prepared from Polygonumorientale
Linn: kinetics, isotherms, pH, and ionic strength studies.
Bioresour Technol 101:5808–5814
88. Weber WJ, Morris JC (1963) Kinetics of adsorption on carbon from
solution. J Sanitary Eng Div - American Soc Civil Eng 89:31–60
89. Wu B, Liu C, Fu C, Wu P, Liu C, Jiang W (2019) Selective sepa-
ration of Cr(VI) and V(V) from solution by simple pH controlled
two-step adsorption/desorption process with ZrO2. Chem Eng J
373:1030–1041. https://doi.org/10.1016/j.cej.2019.05.131
90. Ya V, Martin N, Chou Y-H, Chen Y-M, Choo K-H, Chen S-S, Li
C-W (2018) Electrochemical treatment for simultaneous removal of
heavy metals and organics from surface finishing wastewater using
sacrificial iron anode. J Taiwan Inst Chem Eng 83:107–114. https://
doi.org/10.1016/j.jtice.2017.12.004
91. Yang X, Zhang Z, Kuang S, Wei H, Li Y, Wu G, Geng A, Li Y,
Liao W (2020) Removal of thorium and uranium from leach solu-
tions of ion-adsorption rare earth ores by solvent extraction with
Cextrant 230. Hydrometallurgy 194:105343. https://doi.org/10.
1016/j.hydromet.2020.105343
92. Yavuz Ö, Altunkaynak Y, Güzel F (2003) Removal of Cu, Ni, Co
and Mg from aqueous solution by kaolinite. Water Res 37:948–952
93. Yesil H, Tugtas AE (2020) Removal of heavy metals from leaching
effluents of sewage sludge via supported liquid membranes. Sci
Total Environ 693:133608. https://doi.org/10.1016/j.scitotenv.
2019.133608
94. Yorgun S, Vural N, Dermiral H (2009) Preparation of high-surface
area activated carbons from Paulownia wood by ZnCl2 activation.
Micropourous Mesopourous Mater 122(1-3):189–184. https://doi.
org/10.1016/j.micromeso.2009.02.032
Publisher’s Note Springer Nature remains neutral with regard to jurisdic-
tional claims in published maps and institutional affiliations.