Environmental Processes

https://doi.org/10.1007/s40710-021-00535-x

ORIGINAL ARTICLE

Microporous Erionite-activated Carbon Composite From

Oil Palm Ash for Doxycycline Antibiotic Removal

Waheed Ahmad Khanday 1 & Suhail Ahmad Khanday 2 & Mohd Abbas Shah 1 &
Mohammed Danish 3 & Patrick U. Okoye 4

Received: 30 April 2021 / Accepted: 16 August 2021/

# The Author(s), under exclusive licence to Springer Nature Switzerland AG 2021

Abstract
Microporous erionite-activated carbon (E-AC) composite was synthesized by activating
oil palm ash followed by reacting with aluminum oxide (Al2O3) under alkaline conditions
using hydrothermal method. The Al2O3 was added to the activated palm ash to balance
the excess silica dioxide (SiO2) to obtain the erionite type of zeolite. The E-AC composite
was employed to remove a potent pharmaceutical water pollutant, doxycycline antibiotic
under batch adsorption. The effect of solution pH (3–13), doxycycline initial concentra-
tion, and temperature were screened in the batch study. The E-AC composite revealed
appreciable surface area and average pore size of 467.23 m2/g and 2.765 nm, respectively,
with abundant chemical surface hydroxyl (-OH) and amine (N-H) adsorptive sites. The
textural and surface chemistry greatly contributed to a high monolayer adsorption
capacity of 353.81 mg/g at 50 °C. Also, the Langmuir isotherm with a high R2 of 0.99
for doxycycline adsorption on E-AC sufficiently described the equilibrium data. High
monolayer adsorption capacity of E-AC compared to other adsorbents in the literature
suggests the efficiency of this study. Novel composite synthesis was aimed to enhance the
surface area and to increase the doxycycline removal capacity. These encouraging results
show that the E-AC composite could pave the way for more low-cost composites to be
used as adsorbents for pharmaceutical and other pollutant removals from wastewater.

Keywords Activated carbon . Adsorption . Doxycycline . Erionite . Oil palm ash

* Patrick U. Okoye
ugopaok@ier.unam.mx

1
Department of Chemistry, Government Degree College, 192102 Jammu & Kashmir, India
2
Department of Civil Engineering, National Institute of Technology, Silchar, Assam, India
3
Malaysian Institute of Chemical and Bioengineering Technology, Universiti Kuala Lumpur, Alor
Gajah, 78000 Melaka, Malaysia
4
Instituto de Energías Renovables (IER-UNAM), Privada Xochicalco s/n Col. Centro, Temixco,
Morelos 62580, México
 W. A. Khanday et al.

1 Introduction

Pharmaceuticals in desired chemical formulations are administered to the living creatures to

safeguard their state of health and wellbeing (Grenni et al. 2018). However, these pharma-
ceuticals usually have the composition of chemical molecules of significant contaminating
nature, which have tremendous adverse effects on the environment in particular to the aquatic
ecosystems with more impact on water bodies meant for drinking purposes (Kang et al. 2018).
The broad range of these drugs exist in the form of antimicrobials, also known as antibiotics,
acting against a group of infectious microbes (Peng et al. 2018). When the effluent contam-
inated by these pharmaceuticals enters into the freshwater stream, it causes a potential hazard,
because it could make all the bacteria and microbes resistant to such antibiotics (Wang et al.
2020). Not only this, many of the pharmaceuticals have secondary side effects, for example,
skin irritation, nausea, stomachache and diarrhea (Doxycycline, tetracycline, cephalexin, etc.)
(Ahammad et al. 2021; Oba et al. 2021). Furthermore, a high concentration of doxycycline in
any drinking water body is too dangerous as its overdose is poisonous for human beings (Torki
and Faghihian 2017). These reasons make it necessary for the scientific community to deal
with the pharmaceuticals prior to their release into the environment to avoid antagonistic risks.
A lot of techniques have been employed in the past for pharmaceuticals removal and their
efficient degradation from wastewater, which include photolysis, ozonation, adsorption and
biodegradation (Khanday and Hameed 2018; Liu et al. 2021). The photolysis technique and
other techniques like ozonation are not effective for a wide range of antibiotic treatments. Also,
biodegradation takes time and involves complex processes that result in further production of
toxins in the form of intermediates and mutagens, hence, the more preferred way to treat
pharmaceutical pollutants is adsorption (Elwakeel et al. 2021; Sharma et al. 2017). The
adsorption technique for the removal and treatment of pharmaceuticals is less cumbersome,
and it is cost-effective and safe for the environment. Usage of adsorbents in the form of
activated carbon (AC) for antibiotic pollutant removal nowadays is considered a noteworthy
effort (Jawad et al. 2020; Maia et al. 2021; Zhao et al. 2019). In addition to its high adsorption
capacity, AC has interesting properties such as a well-architectured pore structure and very
high surface area, which make it beneficial for the removal of many pollutants including
pharmaceuticals (Elwakeel et al. 2018; Jang et al. 2018).
To reduce agricultural residue accumulation and handling challenges due to overproduction
and abundance, researchers have tried to convert them into valuable materials, particularly into
ACs for the removal of pollutants (Elwakeel et al. 2015; Ighalo et al. 2021). Such agricultural
wastes which mostly exist in the form of biomass are always beneficial for conversion into
ACs considering their high carbonaceous nature and less un-burnt ash content (Marrakchi et al.
2017). Oil palm ash is a bio-waste that is heaped by processing palm oil in mills upon
combustion of oil palm shells and its fiber, which are used as fuel in a steam boiler. Literature
reports (Khanday et al. 2017) have shown that oil palm ash is abundant in SiO2 (40 %) and
also contains some percentage of Al2O3 (6 % ), which are both essentially needed during
zeolite formation. It is also reported to contain 5.5 % unburned carbon which can be easily
utilized to produce activated carbon.
The present study aimed to convert SiO2 and Al2O3 components of oil palm ash into
Erionite along with simultaneous activation of unburnt carbon present in it to produce Erionite-
activated carbon (E-AC) composite, considering the advantage of using activated carbons and
zeolites in adsorption processes. E-AC composite can find its way as a low-cost adsorbent in
the removal of pharmaceuticals, dyes, and other pollutants from wastewater. Composite
Microporous Erionite-activated Carbon Composite From Oil Palm Ash for...

synthesis was carried out to enhance the surface area and to increase the pharmaceutical
removal capacity. The effects on doxycycline adsorption using E-AC adsorbent with respect to
pH, doxycycline initial concentration, and temperature were studied. Furthermore, the validity
of adsorption data of doxycycline onto E-AC was established via isothermal and kinetic
modeling.

2 Experimental

2.1 Materials

Oil palm ash was obtained from Kerala, India-based oil mill and analytical grade doxycycline
antibiotic (C22H24N2O8, 444.43 g/mol) was supplied by Sigma Aldrich, India. Al2O3 and
NaOH both with ~ 99 % purity were provided by Sigma Aldrich, India. The rest of the
chemicals used in the study were also of analytical grade.

2.2 Production and Structural Analysis of E-AC Composite

Initially, a fixed amount of oil palm ash (10 g) was dissolved in 100 mL of 3 M NaOH solution
and thoroughly stirred for 5 h at 750 rpm. The ash–NaOH slurry was dried in an oven at
around 100 °C for 2 days under still air. Post drying, pyrolysis of NaOH impregnated ash was
carried out in a horizontal reactor made of stainless steel for a fixed time (90 min) and fixed
temperature (600 °C with every 10 °C/min) under nitrogen atmosphere (flow rate 100 mL/min)
to activate the un-burnt carbonaceous matter in the ash. After pyrolysis, the activated ash
sample was washed severally with warm water until neutral pH was obtained. Then, the
activated ash was dried completely and a measured amount of aluminum hydroxide (Al2O3)
was mixed with it. The sample was calculated to achieve desired SiO2/Al2O3 ratio. To maintain
the alkalinity of the mixture, which is necessary for zeolitization, 30 mL of NaOH (2.5 M) was
ran down dropwise with continued stirring and was kept for aging overnight. A hydrothermal
process was adopted to synthesize the zeolite. The mixture was inserted in a stainless-steel
pressure vessel internally lined by teflon and incubated for about 24 h at 110 °C. The activated
carbon-zeolite (denoted as E-AC) composite obtained was rinsed thoroughly with
demineralized water to bring the pH to around 6.5 and was then air-dried to get the dry E-
AC composite samples.
The structural analysis of the synthesized E-AC composite was carried out by X-Ray
Diffraction (XRD). To analyze the surface of E–AC for its morphological characteristics,
SEM images were taken using the Zeiss Supra 35VP instrument. Degassed samples of E–AC
were analyzed for pore diameter and surface area using BET surface area analyzer
(Micromeritics ASAP 2020) and distribution of pores for the sample was calculated using
BJH equation. Functional groups on E–AC prior and after adsorption of doxycycline were
carried out by IR spectrophotometry in 500–4000 cm− 1 range using FTIR USA-Model 2000.

2.3 Adsorption Studies of Doxycycline on E–AC

Doxycycline adsorption studies were evaluated using batch experiments. Initially, doxycycline
solutions prepared in demineralized (DM) water with a varied range of concentrations (50–
400 mg/L) was transferred in stoppered conical flasks of capacity 250 mL and a fixed amount
 W. A. Khanday et al.

of E–AC adsorbent (200 mg = 0.2 g) was added. These flasks were shaken vigorously for
30 h to allow good adsorbent adsorbate contact using a water bath shaker rotating at 150 rpm
while maintaining the temperature of the bath at 30 °C. Small amount of the solution was
pipetted out at regular time intervals to determine the adsorption rate until equilibrium was
achieved. Also, experiments for batch adsorption of doxycycline on E–AC were repeated at 40
and 50 °C to study the temperature effect. The doxycycline solution was subjected to alkaline,
acidic and neutral conditions to observe the effect of varying pH (3 to 13) on its adsorption rate
over E–AC. pH adjustment of the solution was done by drop-wise addition of HCl (0.01 M)
and NaOH (0.01 M) depending on the requirement. Absorption spectroscopy based on Beer-
Lambert law was employed to find out the initial and final concentrations of doxycycline. A
Shimadzu UV/Visible spectrophotometer (double-beam, Model: UV-1700) was used. The
sample was scanned in the wavelength range of 200–500 nm and the lambda max of
doxycycline was found to be 273 nm. The amount of doxycycline adsorbed, qt (mg/g), at
time t was calculated using Eq. (1):
V
qt ¼ ðC 0  C t Þ ð1Þ
W
where Co and Ct are respectively the initial and periodical amounts of doxycycline (mg/L). W
(g) is the mass of E–AC, and V (L) is the volume of the doxycycline sample.
The coefficient of determination (R2) and the root-mean-square error (RMSE) were deter-
mined by applying Eqs. (2) and (3), to identify the best analysis of the adsorption data as
follows:
Pn  2
n¼1 qe;obs  qe;cal
R ¼ 1  Pn 
2
2 ð2Þ
n¼1 qe;obs  qe;obs

! 12
1 X n  2
RMSE ¼ q  qe;cal ð3Þ
n  1 n¼1 e;obs

where qe,obs (mg/g) and qe,cal (mg/g) is the experimental and predicted biosorption uptakes of
doxycycline.

3 Results and Discussion

3.1 Characterization of E–AC

3.1.1 Surface Characteristics

To investigate the crystalline phase, XRD was conducted and is presented in Fig. 1. The XRD
pattern of E-AC composites reveals high-intensity crystalline peaks at 7o, 13.5o, 19o, 24o, and
29.5o, which in comparison to reports available corresponds to erionite-zeolite (Khanday
2017). The XRD pattern also shows an amorphous phase due to the presence of carbon
content in the composite. The distribution of pores in terms of their varying sizes and physical
adsorption isotherms of N2 over the E–AC sample is shown in Fig. 2. Based on the
Microporous Erionite-activated Carbon Composite From Oil Palm Ash for...

nomenclature according to IUPAC, the curve can be classified as type 1 isotherm, which
reflects the synthesized sample to be microporous (Thommes et al. 2015). Observably from the
adsorbent–adsorptive interactions curve, nitrogen uptake at a lower ratio of P/P0 was enhanced
significantly, which gradually flattens into a horizontal plateau and the complete lack of
hysteresis loop suggests micropore dominance in the sample (Liu et al. 2018). In line with
previous experiments, the high-temperature activation for this study was carried out under the
inert atmosphere of N2 gas to enhance the complete burning of volatile matter, which
ultimately led to the formation of a micropore matrix. The E–AC showed a distributed pore
size within 25–50 Å. Moreover, E-AC with a characteristic average pore girth of 27.63 Å, total
pore volume of 0.561 cm3/g, and high surface area of 479.61 m²/g can preferably be a better
choice for removal of antibiotics with intermediate size (Boudrahem et al. 2017). Table 1
shows the surface texture-related parameters of E–AC obtained from isothermal data.

3.1.2 Surface Micrographs and FTIR Spectrum

SEM images taken at different magnifications show flakey zeolite erionite and dense activated
carbon (Fig. 3). Clearly, both erionite and activated carbon contain highly random and uneven
porous structures in E–AC composite. This porous morphology of E–AC is beneficial for the
mass transport of doxycycline molecules to the active sites meant for adsorption. The E–AC
adsorbent’s surface functional groups show peaks at 1,050 cm− 1 and 706 cm− 1, which
correspond to SiO4 or AlO4 asymmetric and symmetric vibration, respectively (Fig. 4)
(Khanday et al. 2014). The peak at 1,640 cm− 1 is associated with the scissoring vibration
of protons within water molecules (Khanday et al. 2016). The broad spectra at 3,430 cm− 1 are
assigned to –OH group stretching modes and the peaks at 1,392 cm− 1 and 2,905 cm− 1 are
assigned to –NH group deformation modes. Hence, the E–AC surface is in surplus of –OH and
N–H functional groups, thus encouraging the adsorption extensively. Upon doxycycline
adsorption, E–AC spectra showed new peak emergence, some peaks shifted and some

Fig. 1 X-ray diffraction pattern of E-AC

 W. A. Khanday et al.

175
Adsorption
Desorption
150

Quantity Adsorbed (cm³/g STP)

125

100

75

50

25

0
0.0 0.2 0.4 0.6 0.8 1.0
Relative Pressure (P/Po)
Fig. 2 BET surface area and pore size distribution of E-AC

characteristic bands vanished and all this affirmed the involvement of functional groups on the
surface of E-AC in doxycycline adsorption (Li et al. 2017).

3.2 E–AC Adsorption Efficiency

3.2.1 Effect of pH of Doxycycline Solution

The adsorption performance shown by E–AC for the removal of doxycycline, with a concen-
tration of 100 mg/L, upon varying the solution pH is presented in Fig. 5. The increase in the
solution pH from 3 to 13 results in a gradual decrease in the uptake of doxycycline by E–AC
from 99.66 mg/g to 63.14 mg/g. This result is a consequence of inter-conversion of antibiotic
doxycycline into differently charged species due to addition and loss of H+ (cation at pH <
2.56, zwitterions at pH 2.56–6.88, and anion at pH > 6.88); thus, it interacts differently with
the surface charge of the adsorbent at varied pH (Kan et al. 2018). Notably, the E-AC
composite possesses hydrophobic sites due to the presence of activated carbon, which interacts
efficiently with the hydrophobic doxycycline zwitterions (Fu et al. 2014). Also, the E–AC is
negatively charged due to the negative framework of zeolite (erionite); hence, it attracts the
positively charged doxycycline cations at low pH, thus showing high adsorption while as

Table 1 Surface area and pore characteristics of E–AC

Surface physical parameters Value

Single point surface area at P/Po = 0.303 (m²/g) 459.26

BET surface area (m²/g) 479.61
Langmuir surface area (m²/g) 639.43
External surface area (m²/g) 356.55
Total pore volume (cm³/g) 0.561
Average pore width (Angstrom, Å) 27.63
Microporous Erionite-activated Carbon Composite From Oil Palm Ash for...

Fig. 3 SEM images of E-AC at 3,000× and 15,000× magnifications

repels the negative doxycycline anions above pH of 7, thereby decreasing the rate of
adsorption uptake (Kan et al. 2018).

3.2.2 Effect of Contact Time and Initial Doxycycline Concentration

A relationship is established between contact time and doxycycline uptake over a varied concen-
tration range of 50–400 mg/L, as shown in Fig. 6. Initially, the adsorption capacity of E–AC for
doxycycline uptake is observed to be high, followed by a gradual decrease until equilibrium was
attained. This is due to the well-established monolayer adsorption phenomenon, as initially there
are many active sites available on E–AC surface for binding doxycycline antibiotic molecules, and
hence, the adsorption is increased, but with time, these sites get masked by the adsorbate

E-AC-Doxycycline
Transmittance (%)

E-AC

1392 706
1638

2905

1050

3430

4000 3500 3000 2500 2000 1500 1000 500

Wavenumber (cm-1)
Fig. 4 FTIR spectra of E-AC before and after adsorption of doxycycline
 W. A. Khanday et al.

120

100

qe (mg/g) 80

60

40

20

0
2 4 6 8 10 12 14
pH
Fig. 5 Solution pH versus Doxycycline uptake of E-AC (V = 100 mL, W = 0.10 g, initial antibiotic
concentration = 100 mg/L, shaking speed = 140 rpm, and temperature = 30 °C)

molecules, thus reducing the adsorption uptake (Boudrahem et al. 2017). Also, the time required
to attain equilibrium is less for lower initial doxycycline concentration (4 h for 50 mg/L) and high
for higher doxycycline concentration (24 h for 200–400 mg/L). This is due to higher active sites
per antibiotic molecule in lower initial doxycycline concentration and lesser active sites per
antibiotic molecule in higher doxycycline concentration. At higher doxycycline concentration,
aggregation of many of these antibiotic molecules into a bulkier species occurs, which hinders
mass transport and diffusion of the adsorbate into the E–AC adsorbent structure (Pap et al. 2017).
High concentration of doxycycline also acts as a driving force to transfer the antibiotic molecules
easily to the binding sites of E–AC due to concentration gradient, which boosts their uptake (Kong
et al. 2017). The high doxycycline uptake of 253 mg/g at the equilibrium time of 24 h was
observed for an initial concentration of 400 mg/L.

3.3 Kinetic Modeling for Doxycycline Adsorption on E-AC

The kinetics allows for the determination of the rate of adsorption from the data obtained via
varying contact time and experimentally obtained adsorbed amount. The obtained plots of
such data are then modelled using the pseudo-second-order (PSO) (Ho and McKay 1999) and
pseudo-first-order (PFO) (Langergen and Svenska 1907) kinetic rate equations, as follows:
 
1
Pseudo  second order qt ¼ k 2 q2e t ð4Þ
1 þ k 2 qe t

 
Pseudo  first order qt ¼ qe 1  ek1 t ð5Þ

where qt (mg/g) is doxycycline uptake at time (t), and k1 (g/mg h) and k2 (1/h) are rate
parameters, which can be determined from the PFO and PSO models, respectively.
The experimentally obtained kinetic data were fitted by employing Eqs. (4) and (5)
followed by regression analysis. Table 2 shows the results. The high R2 and RMSE of the
Microporous Erionite-activated Carbon Composite From Oil Palm Ash for...

300
50 mg/l 100 mg/l 150 mg/l
200 mg/l 300 mg/l 400 mg/l
250

Adsorption uptake (qt) 200

150

100

50

0
0 200 400 600 800 1000 1200 1400 1600 1800
Time (min)

Fig. 6 Effect of initial doxycycline concentration and contact time on Doxycycline adsorption onto E-AC (V =
200 mL, W = 0.20 g, shaking speed of 140 rpm, and Temperature = 30 °C)

PFO model show that the experimental data is highly correlated with the PFO model, which
shows high validity compared with the PSO model. Figure 6 shows the graphs of the measured
and calculated qt values against t at varying inlet concentration of doxycycline (50–400 mg/L).
The PSO model shows an R2 value in the range of 0.95–0.97, which is lower than that of R2 =
0.99 as exhibited by the PFO model. Furthermore, the PSO model exhibits higher (2.3) RMSE
values than the RMSE value of the PFO model (0.9). Therefore, the adequate and accuracy of
the PFO model representation is validated by the R2 value which is close to unity, and its lower
RMSE value compared to that of the PSO model (Wang and Guo 2020), which suggests that
adsorption occurs through diffusion through the interface. Further, with the increase in the inlet
doxycycline concentration, the k1 value shows a dip. This occurs due to an increase in sorbate
molecules per binding site of the adsorbent, which leads to increased competition between
doxycycline molecules for E-AC binding sites, thus, decreasing the diffusion rate and k1 value
(Sayğili and Güzel 2016). The adequacy of the PFO model has also been proven by various
studies related to the adsorption of pharmaceuticals on activated carbon and its composites
(Ahmed et al. 2017).

3.4 Adsorption Isotherm Analysis

Adsorption isotherm at equilibrium in the present study correlates the adsorbed amount of
doxycycline on E-AC with its corresponding residual concentration. The extent and nature of
adsorption were determined by modelling the experimental isotherm data using Langmuir
(1917) and Freundlich (1906) adsorption isotherms as shown in Eqs. (6) and (7):

 
Langmuir isotherm qe ¼ qL KL C e
1þK L C e ð6Þ

1=
Freundlich isotherm qe ¼ K F C e n ð7Þ
 W. A. Khanday et al.

Table 2 PFO and PSO kinetic model parameters for the doxycycline–E–AC system at 30 °C

C0 (mg/l) qe,exp Pseudo-first-order Pseudo-second-order

(mg/g)
qe,cal k1 R2 RMSE qe,cal k2 R2 RMSE
(mg/g) (/min) (mg/g) (g/mg min)

50 46.86 46.23 0.014 0.99 0.263 48.28 5.98E-04 0.95 0.635

100 91.21 92.01 0.012 0.99 0.412 97.23 2.08E-04 0.97 0.986
150 129.83 129.18 0.009 0.99 0.843 141.43 9.84E-05 0.97 3.021
200 165.14 165.87 0.010 0.99 1.320 177.91 7.15E-05 0.96 2.862
300 226.28 225.94 0.009 0.99 1.986 242.74 4.62E-05 0.97 2.917
400 258.3 257.07 0.007 0.99 1.487 273.36 5.43E-05 0.98 3.456

where qe and qL (mg/g) are equilibrium and saturated doxycycline uptake, respectively, Ce
(mg/L) represent the equilibrium concentration of doxycycline, whereas, KL (L/mg), n, and KF
(mg/g).(L/mg)1/n, are constants obtained from the Langmuir and Freundlich models.
The experimentally obtained isothermal data was fitted by employing Eqs. (6) and (7)
followed by regression analysis. The Langmuir model best fitted the experimental data
(Table 3) having a higher R2 of 0.99 than the Freundlich model (0.98). Further, Langmuir
model shows a smaller deviation with RMSE of 0.53–0.96 for measured and computed qe
values of doxycycline than the Freundlich model (0.81–1.39). On the homogeneous surface of
E–AC, doxycycline molecules show monolayer adsorption as is confirmed by the best model
fit (Langmuir isotherm model) (Rai and Singh 2018). However, for the present studied
adsorption system, the Freundlich model with n ˃ 1 describes the preferable adsorption nature
(Marrakchi et al. 2021; Oba et al. 2021). The maximum uptakes of 286.63, 314.34, and
353.81 mg/g from the parameters of the Langmuir model were found for doxycycline at 30 °C,
40 °C, and 50 °C, respectively. The E-AC obtained from the waste oil palm ash precursor
promised a high adsorption capacity towards doxycycline and the increase in adsorption
uptake with temperature for the studied system validates the endothermic nature (Miao et al.
2016).
The E-AC with good surface area presented relatively high adsorption performance for
doxycycline removal, which indicates its suitability as a low-cost bio-adsorbent for the
removal of pharmaceutical molecules as well as various other pollutants from the environment.
Table 4 shows the monolayer adsorption capacity of E-AC is better as compared to other
adsorbents reported in the literature (Abdel Moaty et al. 2020; Brigante and Avena 2016; Liu
et al. 2019; Nieva et al. 2019; Wei et al. 2019; Zhang et al. 2018).

3.5 Thermodynamic Studies

Effect of temperature on doxycycline adsorption on E-AC composite was studied by varying

temperatures over a range of 30–50 oC. It was observed that the increase in temperature results
in an increase in doxycycline adsorption, which shows that its adsorption onto the E-AC
composite is favorable at high temperatures, thus, suggesting the adsorption process to be
endothermic. Such a situation is better explained by thermodynamic adsorption parameters
like enthalpy change (ΔH), Entropy change (ΔS), and Gibb’s free energy change (ΔG) which
are easily determined by change in equilibrium constant K with temperature. Value of K is
obtained from Eq. (8), as follows:
Microporous Erionite-activated Carbon Composite From Oil Palm Ash for...

Table 3 Langmuir and Freundlich isotherm parameters obtained at different temperatures

Temperature (oC) Langmuir isotherm model Freundlich isotherm model

qL (mg/g) kL (L/mg) R2 RMSE kF (mg/g)(L/mg)1/n n R2 RMSE

30 286.63 0.011 0.99 0.96 66.12 1.43 0.98 1.39

40 314.34 0.014 0.99 0.68 75.36 1.41 0.98 0.95
50 353.81 0. 013 0.99 0.53 82.24 1.32 0.98 0.81

C1
K¼ ð8Þ
C2
where C1 is the quantity of doxycycline adsorbed per unit mass of E-AC composite, and C2
is the aqueous phase concentration of doxycycline. From the slope and intercept of Van’t
Hoff plot, thermodynamic parameters like Standard Enthalpy change (ΔHo) and Standard
Entropy change (ΔSo) were determined. In Van’t Hoff plot lnK is plotted against 1/T using
Eq. (9):
So Ho
lnK ¼  ð9Þ
R RT
Standard Gibb’s free energy change (ΔGo) was calculated using Eq. (10):
Go ¼ RTlnK ð10Þ

Thermodynamic parameters for doxycycline adsorption onto E-AC composite are given in
Table 5. Obtained ΔGo values were negative and ΔHo values were positive which confirms
that adsorption of doxycycline onto E-AC composite is spontaneous and endothermic.

3.6 Regeneration and Reusability

Desorption experiments were performed to evaluate the possibility of reusability and regen-
eration of E-AC composite as an adsorbent. Desorption of doxycycline was carried out by a
simple solvent washing technique in which E-AC composite was washed with acidic ethanol
to recover it for next use. The effect of four consecutive adsorption-desorption cycles was

Table 4 Comparison of monolayer adsorption of doxycycline onto various adsorbents

Adsorbents Maximum monolayer adsorption References

capacities (mg/g)

E-AC composite from oil palm ash 353.81 This work

Bio-zeolitic imidazolate framework (ZIF-8) 242.0 Liu et al. (2019)
Bio-sorbents ripe Carica papaya L. peels 215.1 Nieva et al. (2019)
Magnetic porous silicas 200.0 Zhang et al. (2018)
(Fe3O4@SiO2@mSiO2-CD)
Iron loaded sludge biochar 128.9 Wei et al. (2019)
Mesoporous silica 123.5 Brigante and Avena
(2016)
Layered double hydroxides 100.0 Abdel Moaty et al.
(2020)
 W. A. Khanday et al.

Table 5 Thermodynamic parameters of doxycycline adsorption onto E-AC composite

Initial concentration (mg/L) ΔH° (KJ/mol) ΔS° (KJ/K/mol) ΔG° (KJ/mol)

30 oC 40 oC 50 oC

50 13.21 0.08 -9.83 -11.08 -11.07

100 20.17 0.11 -11.01 -13.18 -13.93
150 39.31 0.17 -11.36 -14.92 -16.12
200 66.71 0.23 -11.89 -15.34 -16.33
300 81.12 0.27 -8.97 -10.29 -13.36
400 69.74 0.23 -6.88 -8.41 -9.02

studied, and there was only a slight decrease in the removal efficiency after four cycles of the
adsorption-desorption process, confirming the reusability of E-AC composite for the removal
of doxycycline. Because of high adsorption capability as well as good desorption property, E-
AC composite can be used for commercial applications, especially due to its cost-
effectiveness.

4 Conclusions

Microporous erionite-carbon (E-AC) composite was synthesized successfully by activating oil

palm ash followed by reacting with Al2O3 under alkaline conditions using the hydrothermal
method. The obtained E-AC adsorbent was employed for doxycycline (antibiotics) removal.
E-AC derived from oil palm ash revealed an average pore size of 27.63 Å, a total pore volume
of 0.561 cm3/g, and a high BET surface area of 479.61 m²/g. The Langmuir isotherm with a
high R2 of 0.99 for doxycycline adsorption on E-AC revealed a high monolayer capacity of
353.81 mg/g at 50 °C. Also, the experimental data best fits the first-order kinetic model with
low RMSE in the range of 0.264–1.487 and R2 close to unity. For extensive antibiotic
adsorption, E–AC offered functional multi-sites, and therefore, is a favorable adsorbent for
removal of doxycycline.

Author contributions Waheed Ahmad Khanday: Conceptualization, Methodology and Supervision; Suhail
Ahmad Khanday: Lab work and Data analysis; Mohd Abbas Shah: Graph Plotting and Writing- Original draft
preparation; Mohammed Danish: Writing- Reviewing and Editing; Patrick U. Okoye: Writing- Reviewing and
Editing, Supervision.

Data Availability All the data generated or analyzed in this study are included in this published article.

Declarations The authors declare that they have no known competing financial interests or personal
relationships that could have appeared to influence the work reported in this paper.

References

Abdel Moaty SA, Mahmoud RK, Mohamed NA, Gaber Y, Farghali AA, Abdel Wahed MSM, Younes HA
(2020) Synthesis and characterisation of LDH-type anionic nanomaterials for the effective removal of
doxycycline from aqueous media. Water Environ J 34:290–308
Microporous Erionite-activated Carbon Composite From Oil Palm Ash for...

Ahammad NA, Zulkifli MA, Ahmad MA, Hameed BH, Mohd Din AT (2021) Desorption of chloramphenicol
from ordered mesoporous carbon-alginate beads: Effects of operating parameters, and isotherm, kinetics, and
regeneration studies. J Environ Chem Eng 9:105015. https://doi.org/10.1016/j.jece.2020.105015
Ahmed MJ, Islam MA, Asif M, Hameed BH (2017) Human hair-derived high surface area porous carbon
material for the adsorption isotherm and kinetics of tetracycline antibiotics. Bioresour Technol 243:778–784.
https://doi.org/10.1016/j.biortech.2017.06.174
Boudrahem N, Delpeux-Ouldriane S, Khenniche L, Boudrahem F, Aissani-Benissad F, Gineys M (2017) Single
and mixture adsorption of clofibric acid, tetracycline and paracetamol onto Activated carbon developed from
cotton cloth residue. Process Saf Environ Prot 111:544–559. https://doi.org/10.1016/j.psep.2017.08.025
Brigante M, Avena M (2016) Biotemplated synthesis of mesoporous silica for doxycycline removal. Effect of
pH, temperature, ionic strength and Ca2+ concentration on the adsorption behaviour. Microporous
Mesoporous Mater 225:534–542. https://doi.org/10.1016/j.micromeso.2016.01.035
Elwakeel KZ, El-Sayed GO, Abo El-Nassr SM (2015) Removal of ferrous and manganous from water by
activated carbon obtained from sugarcane bagasse. Desalin Water Treat 55:471–483
Elwakeel KZ, Aly MH, El-Howety MA, El-Fadaly E, Al-Said A (2018) Synthesis of Chitosan@activated carbon
beads with abundant amino groups for capture of Cu(II) and Cd(II) from aqueous solutions. J Polym Environ
26:3590–3602. https://doi.org/10.1007/s10924-018-1243-2
Elwakeel KZ, Elgarahy AM, Al-Bogami AS, Hamza MF, Guibal E (2021) 2-Mercaptobenzimidazole-
functionalized chitosan for enhanced removal of methylene blue: Batch and column studies. J Environ
Chem Eng 9:105609
Freundlich HMF (1906) über die adsorption in losungen (Adsorption in Solution). Zeitschrift für Phys Chemie
57:385–490
Fu K, Yue Q, Gao B, Sun Y, Wang Y, Li Q, Zhao P, Chen S (2014) Physicochemical and adsorptive properties
of activated carbons from Arundo donax Linn utilizing different iron salts as activating agents. J Taiwan Inst
Chem Eng 45:3007–3015. https://doi.org/10.1016/j.jtice.2014.08.026
Grenni P, Ancona V, Barra A (2018) Ecological effects of antibiotics on natural ecosystems: A review.
Microchem J 136:25–39. https://doi.org/10.1016/j.microc.2017.02.006
Ho YS, McKay G (1999) Pseudo-second order model for sorption processes. Process Biochem 34:451–465.
https://doi.org/10.1016/S0032-9592(98)00112-5
Ighalo JO, Igwegbe CA, Aniagor CO, Oba SN (2021) A review of methods for the removal of penicillins from
water. J Water Process Eng 39:101886. https://doi.org/10.1016/j.jwpe.2020.101886
Jang HM, Yoo S, Choi Y-K, Park S, Kan E (2018) Adsorption isotherm, kinetic modeling and mechanism of
tetracycline on Pinus taeda-derived activated biochar. Bioresour Technol 259:24–31. https://doi.org/10.
1016/j.biortech.2018.03.013
Jawad AH, Abdulhameed AS, Mastuli MS (2020) Mesoporous crosslinked chitosan-activated charcoal compos-
ite for the removal of thionine cationic dye: comprehensive adsorption and mechanism study. J Polym
Environ 28:1095–1105. https://doi.org/10.1007/s10924-020-01671-5
Kan Y, Yue Q, Liu S, Gao B (2018) Effects of Cu and CuO on the preparation of activated carbon from waste
circuit boards by H3PO4 activation. Chem Eng J 331:93–101. https://doi.org/10.1016/j.cej.2017.08.113
Kang AJ, Brown AK, Wong CS, Yuan Q (2018) Removal of Antibiotic Sulfamethoxazole by Anoxic /
Anaerobic / Oxic Granular and Bioresour Technol 251, 151–157. https://doi.org/10.1016/j.biortech.2017.
12.021
Khanday WA (2017) Dynamic cum batch adsorption of a vesicant CWA (2-chloroethyl ethyl sulfide) over
synthetic erionite. Microporous Mesoporous Mater 244:15–20
Khanday WA, Hameed BH (2018) Zeolite-hydroxyapatite-activated oil palm ash composite for antibiotic
tetracycline adsorption. Fuel 215:499–505
Khanday WA, Majid SA, Chandra Shekar S, Tomar R (2014) Dynamic adsorption of DMMP over synthetic
zeolite-Alpha. Arab J Chem 7:115–123. https://doi.org/10.1016/j.arabjc.2013.06.026
Khanday WA, Kabir G, Hameed BH (2016) Catalytic pyrolysis of oil palm mesocarp fibre on a zeolite derived
from low-cost oil palm ash. Energy Convers Manag 127:265–272
Khanday WA, Marrakchi F, Asif M, Hameed BH (2017) Mesoporous zeolite–activated carbon composite from
oil palm ash as an effective adsorbent for methylene blue. J Taiwan Inst Chem Eng 70:32–41. https://doi.org/
10.1016/j.jtice.2016.10.029
Kong Q, He X, Shu L, Miao M (2017) Ofloxacin adsorption by activated carbon derived from luffa sponge:
Kinetic, isotherm, and thermodynamic analyses. Process Saf Environ Prot 112:254–264. https://doi.org/10.
1016/j.psep.2017.05.011
Langergen S, Svenska BK (1907) Zur Theorie der sogenannten Adsorption gelöster Stoffe. Zeitschrift für
Chemie Ind der Kolloide 2:15. https://doi.org/10.1007/BF01501332
Langmuir I (1917) The constitution and fundamental properties of solids and liquids. J Franklin Inst 183:102–
105. https://doi.org/10.1016/S0016-0032(17)90938-X
 W. A. Khanday et al.

Li J, Jiang B, Liu Y, Qiu C, Hu J, Qian G, Guo W, Ngo HH (2017) Preparation and adsorption properties of
magnetic chitosan composite adsorbent for Cu2 + removal. J Clean Prod 158:51–58. https://doi.org/10.1016/
j.jclepro.2017.04.156
Liu Y, Zhao Y, Li K, Wang Z, Tian P, Liu D, Yang T, Wang J (2018) Activated carbon derived from chitosan as
air cathode catalyst for high performance in microbial fuel cells. J Power Sources 378:1–9. https://doi.org/10.
1016/j.jpowsour.2017.12.019
Liu J, Li J, Wang G, Yang W, Yang J, Liu Y (2019) Bioinspired zeolitic imidazolate framework (ZIF-8)
magnetic micromotors for highly efficient removal of organic pollutants from water. J Colloid Interface Sci
555:234–244
Liu Y, Zhao Y, Wang J (2021) Fenton/Fenton-like processes with in-situ production of hydrogen peroxide/
hydroxyl radical for degradation of emerging contaminants: advances and prospects. J Hazard Mater 404:
124191. https://doi.org/10.1016/j.jhazmat.2020.124191
Maia LS, da Silva AIC, Carneiro ES, Monticelli FM, Pinhati FR, Mulinari DR (2021) Activated Carbon From
Palm Fibres Used as an Adsorbent for Methylene Blue Removal. J Polym Environ 29:1162–1175. https://
doi.org/10.1007/s10924-020-01951-0
Marrakchi F, Ahmed MJ, Khanday WA, Asif M, Hameed BH (2017) Mesoporous-activated carbon prepared
from chitosan flakes via single-step sodium hydroxide activation for the adsorption of methylene blue. Int J
Biol Macromol 98:233–239. https://doi.org/10.1016/j.ijbiomac.2017.01.119
Marrakchi F, Zafar FF, Wei M, Wang S (2021) Bioresource Technology Cross-linked FeCl 3 -activated seaweed
carbon / MCM-41 / alginate hydrogel composite for effective biosorption of bisphenol A plasticizer and
basic dye from aqueous solution. Bioresour Technol 331:125046. https://doi.org/10.1016/j.biortech.2021.
125046
Miao M-S, Liu Q, Shu L, Wang Z, Liu Y-Z, Kong Q (2016) Removal of cephalexin from effluent by activated
carbon prepared from alligator weed: Kinetics, isotherms, and thermodynamic analyses. Process Saf Environ
Prot 104:481–489. https://doi.org/10.1016/j.psep.2016.03.017
Nieva AD, Buenafe RJQ, Orense LMS, Trinidad JMR (2019) Biosorption of doxycycline using Carica papaya L.
peels. In: IOP Conference Series: Earth and Environmental Science. IOP Publishing, Bristol, p12010
Oba SN, Ighalo JO, Aniagor CO, Igwegbe CA (2021) Removal of ibuprofen from aqueous media by adsorption:
A comprehensive review. Sci Total Environ 780:146608. https://doi.org/10.1016/j.scitotenv.2021.146608
Pap S, Šolević Knudsen T, Radonić J, Maletić S, Igić SM, Turk Sekulić M (2017) Utilization of fruit processing
industry waste as green activated carbon for the treatment of heavy metals and chlorophenols contaminated
water. J Clean Prod 162:958–972. https://doi.org/10.1016/j.jclepro.2017.06.083
Peng X, Hu F, Zhang T, Qiu F, Dai H (2018) Amine-functionalized magnetic bamboo-based activated carbon
adsorptive removal of ciprofloxacin and norfloxacin: A batch and fixed-bed column study. Bioresour
Technol 249:924–934. https://doi.org/10.1016/j.biortech.2017.10.095
Rai P, Singh KP (2018) Valorization of Poly (ethylene) terephthalate ( PET ) wastes into magnetic carbon for
adsorption of antibiotic from water: Characterization and application. J Environ Manage 207:249–261.
https://doi.org/10.1016/j.jenvman.2017.11.047
Sayğili H, Güzel F (2016) Effective removal of tetracycline from aqueous solution using activated carbon
prepared from tomato (Lycopersicon esculentum Mill.) industrial processing waste. Ecotoxicol Environ Saf
131:22–29. https://doi.org/10.1016/j.ecoenv.2016.05.001
Sharma V, Kumar V, Pakshirajan R, Pugazhenthi K (2017) Integrated adsorption-membrane filtration process for
antibiotic removal from aqueous solution. Powder Technol 321:259–269. https://doi.org/10.1016/j.powtec.
2017.08.040
Thommes M, Kaneko K, Neimark AV, Olivier JP, Rodriguez-Reinoso F, Rouquerol J, Sing KSW (2015)
Physisorption of gases, with special reference to the evaluation of surface area and pore size distribution
(IUPAC Technical Report). Pure Appl Chem 87:1051–1069. https://doi.org/10.1515/pac-2014-1117
Torki F, Faghihian H (2017) Sunlight-assisted decomposition of cephalexin by novel synthesized NiS-PPY-
Fe3O4 nanophotocatalyst. J Photochem Photobiol A Chem 338:49–59. https://doi.org/10.1016/j.jphotochem.
2017.02.003
Wang J, Chu L, Wojnárovits L, Takács E (2020) Occurrence and fate of antibiotics, antibiotic resistant genes
(ARGs) and antibiotic resistant bacteria (ARB) in municipal wastewater treatment plant: an overview. Sci
Total Environ 744:140997. https://doi.org/10.1016/j.scitotenv.2020.140997
Wang J, Guo X (2020) Adsorption kinetic models: Physical meanings, applications, and solving methods. J
Hazard Mater 390:122156
Wei J, Liu Y, Li J, Zhu Y, Yu H, Peng Y (2019) Adsorption and co-adsorption of tetracycline and doxycycline
by one-step synthesized iron loaded sludge biochar. Chemosphere 236:124254
Zhang Y, Jiang F, Huang D, Hou S, Wang H, Wang M, Chi Y, Zhao Z (2018) A facile route to magnetic
mesoporous core–shell structured silicas containing covalently bound cyclodextrins for the removal of the
antibiotic doxycycline from water. RSC Adv 8:31348–31357
Microporous Erionite-activated Carbon Composite From Oil Palm Ash for...

Zhao D, Deng Y, Han D, Tan L, Ding Y, Zhou Z, Xu H, Guo Y (2019) Exploring structural variations of
hydrogen-bonding patterns in cellulose during mechanical pulp refining of tobacco stems. Carbohydr Polym
204:247–254. https://doi.org/10.1016/j.carbpol.2018.10.024

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