Desalination and Water Treatment 174 (2020) 361–375

January
www.deswater.com
doi: 10.5004/dwt.2020.24864

Uptake of crystal violet from water by modified Khalas dates residues

Muneera Abdullah Alfrhana, Hassan H. Hammuda,*, Mohammed A. Al-Omaira,

Mervat A. El-Sonbatib
a
Department of Chemistry, College of Science, King Faisal University, Al-Hassa 31982, Saudi Arabia,
emails: [email protected] (H.H. Hammud), [email protected] (M.A. Alfrhan), [email protected] (M.A. Al-Omair)
b
Environmental Sciences Department, Faculty of Science, Damietta University, Egypt, email: [email protected]

Received 7 March 2019; Accepted 5 September 2019

abstract
Removal of crystal violet dye (CV) from polluted water was studied by adsorption techniques.
Adsorbents were prepared from waste residue available from syrup date industrial residue (SDIR).
The SDIR from Khalas dates residue (KR) were modified by chemical treatment with formaldehyde
to give KF, and with calcium chloride to give KC adsorbents. The characteristic of adsorbents was
determined by Fourier-transform infrared spectroscopy (FTIR), scanning electron microscopy and
thermogravimetric analysis. The optimum conditions were determined in batch experiments for the
best uptake of crystal violet CV by adsorbents. The results showed that the adsorption data was well
described by both Langmuir and Freundlich more than Temkin and followed the pseudo-­second-
order equation. Langmuir maximum capacity q (mg g–1) for KF was found 144.49  mg  g–1, while it
was 108.25 and 89.31 mg g–1 for KC and KR respectively. Thermodynamic and activated thermody-
namic parameters were determined for the uptake of crystal violet and this study shows that the
adsorption process is exothermic and spontaneous. The column breakthrough curve capacity was
determined for the uptake of crystal violet by modified SDIR. It was found that Thomas and Yoon-
Nelson column kinetics models describe best the experimental kinetic data, and the obtained capacity
was 136.58 mg g–1 for KF and 89.11 mg g–1 for KC. The results prove that the SDIR (raw and treated)
could be used as an effective and economical adsorbent for dye removal from wastewater.
Keywords: Adsorption; Crystal violet; Syrup date manufacture residue; Equilibrium; Kinetics;
Thermodynamics

1. Introduction dissolved oxygen since it contains high values of biochem-

ical oxygen demand and chemical oxygen demand causing
Crystal Violet (CV), a triphenylmethane dye has been
an environmental problem to reservoirs receiving the waste-
extensively used as a biological stain. It is used to hinder
water [4].
fungal growth in poultry feed and as a skin disinfectant in
However, CV can cause skin and digestive tract inflam-
human beings [1]. The CV is also used for dyeing nylon,
mation and respiratory and kidney failure. It is also car-
wool, plastics, gasoline, varnish, fat, oil and waxes [2,3].
cinogenic, it increases the risk of human bladder cancer
The textile industry produces a large number of efflu-
[5,6]. The CV has considered as hazardous compound and
ents and wastewater in the dyeing process which contains a
its use was prohibited in the aquaculture and food industry.
massive amount of coloring agents and toxic undegradable
Several studies indicated that CV dye has carcinogenic and
substances. The textile wastewater with high CV dye has low
mutagenic effects in rodents and fishes [7], hinders seed

* Corresponding author.

1944-3994/1944-3986 © 2020 Desalination Publications. All rights reserved.

362 M.A. Alfrhan et al. / Desalination and Water Treatment 174 (2020) 361–375

germination, causes a decrease in root and shoot length of 0.2 M sodium carbonate Na2CO3 solution, and finally with
plant species and retards the activity of microbes contribut- distilled water. The pre-treated materials were then dried at
ing to soil fertility [8]. 60°C for 24  h to give the adsorbent KF (KR modified with
Thus, its remediation becomes the interest of many formaldehyde) [17].
researchers. Adsorption is superior to other separation
techniques because it is efficient, economically feasible and 2.2. Batch mode adsorption study procedure
capable to separate a range of pollutants. Moreover, adsor-
bent materials from agricultural and food industry are abun- The isotherms experiments were performed by using
dant and have a very low cost. Also, chemical modification 250  mL conical flasks containing 0.1  g adsorbent KR or its
of biomass can give extra stability, durability and reuse for modified forms KF and KC and 100 ml crystal violet solution
multiple cycles. It also give extra functional groups that (pH = 5.5) in different initial concentrations (50, 100, 150, 200,
increase the uptake capacity. Several biomass adsorbents 250, 300, 400, and 500  ppm) under the controlled tempera-
were studied for CV adsorption. Examples are an aquatic ture in a shaker incubator with constant speed of 160  rpm
plant “Water hyacinth” [3], citric acid modified rice straw for 4  h. In a batch system, the effect of several parameters
[9], NaOH-modified rice husk [10], sugarcane bagasse [11], was studied such as temperature, sorbate concentration,
H2SO4 modified sugarcane bagasse [12], protonated water- sorbent dose, contact time and pH. At the desired time, the
melon [13]. sodium carbonate modified Bambusa tulda [14] concentration of the dye (CV) in solution was obtained by
Thus, in the present work, we adopt adsorption tech- using Ultraviolet-Visible (UV-VIS) Spectrophotometer at
niques using “Khalas” Palm fiber waste residue from 590 nm, and the capacity (amount of dye (mg) removed by
date syrup industries and its chemically modified form to 1 g of adsorbent) can be calculated.
efficiently remove the pollutant crystal violet from water. In the kinetics experiments, 0.1  g of adsorbent were
The following is undertaken to achieve the aim of the placed into 250 Erlenmeyer flask containing 100 ml of
work: Chemical modification of date residues to prepare 50 or 100  ppm dye solution. The mixture was shaken, and
adsorbents, find the optimum condition for best uptake the remaining dye concentration was measured at 30  min
of crystal violet, test the ability of prepared adsorbents to intervals for a total of 240  min. The experiments were car-
uptake crystal violet from water using batch and column ried out at different temperatures to calculate the activated
techniques. thermodynamics parameters.

2.3. Column mode adsorption study procedure

2. Experimental setup
The dynamic adsorption system is important for study-
2.1. Chemicals and adsorbents ing the efficiency of a larger quantity of sorbent materials
All chemicals used were of analytical reagent grade for removing sorbate from wastewater. The column study
quality and were stored under dry conditions. Stock solu- was carried using a Pyrex glass column of 30  cm length
tions of calcium chloride, sodium carbonate, sodium acetate, and 1.3 cm internal diameter. A 1 g of sorbent was packed
sodium hydroxide, and crystal violet dye were prepared into column then a standard solution of 200  ppm of CV
by dissolving appropriate weight in double-distilled water. was passed through the column with flow rate 1 ml min–1.
Formaldehyde (34.5%), hydrochloric acid (37%), and acetic The effluent samples were collected at a different time and
acid (100%) were also diluted for further use. Crystal violet the dye concentration in the effluent was determined using
dye (CV) has a chemical formula C25H30N3Cl, molar mass: a UV-VIS spectrophotometer. Initially, the concentration
407.979 g mol–1, CAS:548-62-9, and melting point 205°C [15]. of dye in the effluent is negligible, then the concentration
The adsorbent Khalas dates residue (KR) from the man- increases gradually until the column becomes saturated.
ufacturing of Khalas syrup date by Al-Ahsa Food Industries This occurred when the concentration of the dye in the
Co. Ltd., (Hofuf, Saudi Arabia) is used as adsorbent of CV effluent equal the initial concentration of dye (200  ppm).
dye. KR was dried in an air-oven (model 30 Lab Oven) at For another adsorption cycle, the column was regener-
105°C for 22  h. The dried materials were grounded and ated by 0.3  M HCl as an eluent solution with a flow rate
sieved with 1  mm particle size sieve and then stored in an of 1 ml min–1. The column was then washed with distilled
airtight container for further use and modification. water until a pH  =  5.5 to make sure the disposal of the
Modification of KR with calcium chloride CaCl2:10.0 g remnants of acid before starting a new cycle.
of dried biomass of KR was treated with 400  ml of 0.2  M
CaCl2 solution at pH 5.5. The mixture was shaken for 12 h on 3. Results and discussion
a shaker incubator at 160 rpm, at 25°C. The biomass samples
were filtered and washed with distilled water to eliminate 3.1. Adsorbent characterization
extra calcium chloride and then dried in an air oven at 60°C 3.1.1. Fourier-transform infrared spectroscopy
for 24 h to give the adsorbent KC (KR modified with calcium
chloride) [16,17]. Fourier-transform infrared spectroscopy (FTIR) spec-
Modification of KR with formaldehyde: 70  ml of form- tra can give information about the nature of date residues
aldehyde (34.5%) and 135  ml of 0.1  M hydrochloric acid functional groups responsible for the adsorption process.
HCl solutions were added to 10.0  g of dried biomass KR. The spectra before and after modification are recorded for
The mixture was stirred for 24 h. The biomass materials were three types of date residues (Fig. 1). The data listed in Table 1
then filtered, washed with double distilled water, then with indicates that the adsorbent surface is complex. Infrared (IR)
 M.A. Alfrhan et al. / Desalination and Water Treatment 174 (2020) 361–375 363

FTIR of Khlas dates residues

120

KF
100

KC
80

KR
60

40

20

0
0 500 1000 1500 2000 2500 3000 3500 4000 4500

Raw residue KR Formaldehyde residue KF CaCl2 residue KC

Fig. 1. FTIR spectra for KR raw, KF modified with formaldehyde, KC modified with calcium chloride before and KR*, KF*, KC* after
CV adsorption.

absorption peaks of functional groups for cellulose, hemi- chemical interaction between dye and adsorbent surface,
cellulose, and lignin indicate that date residues are capable for example, the broad peak at 3,306.69  cm–1 for KR were
of effective adsorption of dyes [18]. The broad stretching shifted to higher wavenumber 3,339.98  cm–1. The shifting
vibration peak of KR at about 3,306.69  cm–1 is due to the of O–H, N–H and <C=O stretching vibrations indicates that
hydroxyl O–H group of cellulose and N–H group of amine. hydroxyl, amine, and carbonyl groups were involved in CV
Carbonyl groups and aromatic rings show peaks at 1,718.68 adsorption. The new peaks at 1,583.5 and 1,362.6  cm–1 in
[19] and 1,618.13 cm–1. The strong C–O peak at 1,025.5 cm–1 KR* after dye loading, are due to aromatic and C–N groups
confirms the existence of the cellulose structure. The peak characteristic of CV. Jain and Jayaram described that the
at 1,244.25 cm–1 was due to C–N stretching vibration. Small hydroxyl group in the adsorbent and nitrogen atom in the
peaks from 600 to 800 cm–1 indicate aromatic compounds amine group in CV were involved in adsorption through
with out of plane C–H stretching band modes. weak H-bond.
IR peaks of KR after CV adsorption KR* shows shift The FTIR spectra of KR modified with Formaldehyde
compared to raw materials KR (Table 1). This shift confirms KF Fig. 1 proved successful modification by formaldehyde

Table 1
FTIR spectral data for KR raw, KF modified with KF, KC modified with calcium chloride before and KR*, KF*, KC* after CV adsorption

Stretching vibrations, wave number (cm–1)

Functional group KR KR* KF KF* KC KC*
(O–H), (N–H) 3,306.69 3,339.98 3,294.8 3,314.68 3,334.91 3,340.94
(C–H) 2,919.36 2,916.61 2,918.13 2,917.64 2,917.3 2,918.42
2,861.10 2,849.3 2,851.0 2,850.39 2,850.09 2,851.89
(C=O) 1,718.68 1,734.25 1,724.81 1,718.96 1,718.94 1,733.88
(C=C) 1,618.13 1,607.4 1,624.38 1,610.61 1,617.88 1,624.31
(C–N) 1,244.25 1,233.93 1,240.28 1,233.27 1,238.67 1,236.77
(C–O–C) 1,149.70 1,162.20 1,156.12 1,164.32 1,156.12 1,162.79
1,025.50 1,029.25 1,029.25 1,027.20 1,027.26 1,027.16
364 M.A. Alfrhan et al. / Desalination and Water Treatment 174 (2020) 361–375

due to shifting of peaks at 1,719 cm–1 belonging to <C=O group reflected the existence of aromatic ring and C–N group of
to around 1,724 cm–1. The great shifting of IR wavenumbers CV (Table 1).
between formaldehyde modified KR and formaldehyde
modified KR after adsorption of CV KF* suggests chemical 3.1.2. Scanning electron microscopy analysis
adsorption of dye with the involvement of hydroxyl, amino,
and carboxyl groups. Also, new peaks appeared for KF* Scanning electron microscopy (SEM) is a primary instru-
at 1,582.3; 1,355.8; and 1,162.5  cm–1 due to adsorbed CV ment to characterize the surface morphology of adsorbent.
dye (Fig. S1, Table 1). Functional groups peaks of KC at The SEM images of KR, KF, and KC before and KR*, KF*
3,334.91; 1,718.94; 1,617.88; and 1,156.12  cm–1 are shifted in and KC* after crystal violet adsorption were done using SEM
CaCl2 modified KR after adsorption of CV KC* to 3,340.94; (Jeol model 6360 LVSEM, USA), with a scale ranging from
1,733.88; 1,624.31; and 1,162.79 cm–1 indicating occurrence of 10 to 100  mm. The results are shown in Fig. 2. All materi-
chemical interactions in the adsorption process. New peaks als before adsorption have an irregular surface with some
also appear at 1,584 and 1,362 cm–1 after adsorption of dye pores and cavities that enhance their ability for adsorption.

a. KR b. KR*

c. KC d. KC*

e. KF f. KF*

Fig. 2. SEM images (a,c,e) of KR raw, KC modified with calcium chloride, and KF modified with formaldehyde before adsorption, and
(b,d,f) KR*, KC* and KF* after adsorption of CV.
 M.A. Alfrhan et al. / Desalination and Water Treatment 174 (2020) 361–375 365

Modified material KC and KF are more porous and thus Effect of temperature: Adsorption process of crystal vio-
have more potential for adsorption than raw material KR let by different dates residues was studied at different tem-
[21]. The surface morphology was changed in KF compared peratures (25°C, 30°C, 35°C, and 40°C) with a mixture of
to KR. KF microstructure showed the formation of hollow 0.1 g adsorbent into 100 ml (100 ppm) dye solution for 4 h.
rings as a result of the polymerization of raw materials by The results indicated that the percentage removal of dye
formaldehyde (Fig. 2). Obviously, after CV adsorption, the decreases with increased temperature of the system and that
surface is fully covered by crystal violet (white spots) where the greatest % removal of KF 95% occurred at 25°C. This
the surface becomes less porous [22]. result suggests that the adsorption process is exothermic.
A similar trend was reported by Chandra et al. [27] using
3.1.3. Thermogravimetric analysis activated carbon prepared from durian shell to remove meth-
ylene blue from aqueous solution. There are weakening in
Thermogravimetric analysis (TGA) study of KF, KR and the bonds between the dye and the active sites of adsorbent
KC were done using Shimadzu TGA-50H (Japan) thermal as the temperature increase. Moreover at high temperature,
analyzer under the nitrogen environment by heating from the solubility of dye increases which increases the interaction
room temperature 25°C to 600°C at a heating rate of 15 min–1. between solute and solvent more than between solute and
Several stages of degradation were obtained. The first stage adsorbent [28].
of decomposition for KR occurred in the range from 25°C to
100°C which involved evaporation of moisture with weigh
3.3. Adsorption isotherms
loss approximately (10.9%). Similar weight loss was reported
by White et al. [23] for the evaporation of moisture from Adsorption isotherms parameters describe the distri-
agriculture fibers. The second and last stage for KR occurred bution of CV among two phases between solid and liquid
between 100°C–360°C corresponds to a loss of all organic phases, surface properties of adsorbent at equilibrium con-
materials with weight loss equal to 41.1%. dition and adsorption capacity of the material. The linear
The first stage of loss of moisture (10.6%) of KF was fol- and nonlinear isotherm models were applied at 25°C, 30°C,
lowed by the second and third stages of mass loss. These 35°C, and 40°C for Langmuir, Freundlich, and Temkin mod-
occurred at 100°C–200°C and at 200°C–280°C respectively, els [16,17]. The best model is the one with higher correlation
because of degradation of cellulose and hemicellulose coefficients R2 and lower Chi-square test c2 and the sum of
with mass loss (5.3%) and (8.6%) respectively [24]. The last squared residuals (SSR) values for adsorption of CV by six
decomposition between 280°C to 440°C (38.61%) is due to types of syrup date industrial residue (SDIR) [16,17,29–32].
lignin since decomposition of lignin is more difficult then Linear and nonlinear Langmuir, Freundlich and Temkin
cellulose and hemicellulose [25]. constants and parameters for adsorption of CV by KR, KF,
While KC has almost no water loss in the first stage. and KC at 303  K are listed in Table 2. While the results of
The second stage occurred between 150°C–250°C with the nonlinear isotherm model of KR modified with form-
weight loss of 4.62% while the third stage occurred between aldehyde KF at different temperatures are presented in
250°C–420°C with weight loss of 48%. Table S1. The Langmuir linear plots for adsorption of CV
The last step which corresponds to major organic material onto KF and KC at 303 K are shown in Fig. 3. Temkin non-
loss has shifted to higher temperature values (250°C–440°C) linear plots of CV uptake by KC at 303  K are shown in
in the case of KF and KC compared to (100°C–360°C) for Fig. S2. The Langmuir maximum capacity uptake q (mg g–1)
KR. The increased thermal stability indicates that chemical was found to decrease in the order KF, KC, and KR as such
modification of date residues has occurred. 144.49, 108.25, and 87.5 9  mg  g–1 respectively, at 303  K. It
was found that both Langmuir and Freundlich models are
fitting the experimental data more than Temkin in most
3.2. Effect of different parameters on uptake of
case, in terms of correlation coefficient close to 1.0 and low
crystal violet by syrup date industrial residue
χ2 and SSR values. Langmuir favors monolayer adsorption
Effect of agitation time and initial concentration: For all onto specific homogeneous sites, while Temkin describes
solutions studied containing 0.1 g adsorbent in 100 ml CV multilayer adsorption onto heterogeneous sites of the
dye solution (50, 100, 200, 300, 400, and 500 ppm) and shaken adsorbent. Besides, it is observed from Table 2 that the val-
at 160 rpm, the % removal of CV by KF increases rapidly at ues of RL (separation factor) is between 0 and 1. This indi-
initial times. However, it was observed that percent removal cates favorable adsorption for overall results [33]. Similar
of crystal violet has little change after 180 min and at 240 min results were obtained for adsorption of CV by treated ginger
equilibrium is attained. waste and date palm leaflets [34,35]. Moreover, the values of
Effect of the mass of adsorbent: The effect of adsorbent Freundlich constant (n) for all adsorbents are greater than 1,
dosage of KF on percent removal of crystal violet solution indicating strong adsorption between adsorbate and adsor-
100 ml with concentration 100 ppm at 25°C was investigated bent at all studied temperatures [36]. Freundlich’s constant
using the different mass of (0.03, 0.05, 0.07, 0.1, 0.15, and 0.2 g) KF is greatest in the case of KF adsorbent.
shaken at 160 rpm for hours. The percent removal of crystal Temkin equilibrium binding constant KT (L g–1) and heat
violet increase initially with an increase in the dose of KF due of adsorption BT are also highest for KF adsorbent, where the
to an increase in surface area available of adsorbent sites, but degree of adsorption for the Temkin model depends on the
after 0.1 g of adsorbent, no significant increment was noted in chemical nature and specific surface area of the adsorbent,
the removal of dye because all sites have been fully occupied and chemical nature, temperature, and concentration of the
[26]. Thus the optimum mass of KF was achieved at 0.1 g. adsorbate. It was found that the capacity decreases with an
366 M.A. Alfrhan et al. / Desalination and Water Treatment 174 (2020) 361–375

Table 2
Langmuir, Freundlich, and Temkin linear and non-linear model parameters for adsorption of 100 ml of crystal violet (50–500 ppm)
by 0.1 g of KR, KF and KC at 303 K

Adsorbent Langmuir Freundlich Temkin

Parameters Linear Non-linear Parameters Linear Non-linear Parameters Non-linear
KR qmax (mg g ) –1
89.31 87.5 9 KF (mg g ) × (L mg )
–1 –1 1/n
20.92 20.17 KT (L g )
–1
0.8911
KL (L mg–1) 0.0249 0.036 n 4.388 4.2 BT (J mol–1) 13.76
R2 0.976 0.976 R2 0.940 0.931 R2 0.911
χ2 0.0926 16.98 χ2 0.0072 28.70 χ2 37.27
SSR 0.3704 50.92 SSR 0.0288 115.10 SSR 149.09
RL 0.0743 0.0526
KF qmax (mg g–1) 138.73 144.49 KF (mg g–1) × (L mg–1)1/n 34.38 35.26 KT (L g–1) 1.57
KL (L mg–1) 0.0566 0.086 n 4.139 4.12 BT (J mol–1) 22.41
R2 0.989 0.964 R2 0.957 0.955 R2 0.951
χ2
0.0146 90.65 χ 2
0.0187 83.07 χ2
90.16
SSR 0.0587 271.96 SSR 0.0751 332.28 SSR 360.64
RL 0.0341 0.0227
KC qmax (mg g ) –1
109.36 108.25 KF (mg g–1) × (L mg–1)1/n 20.98 21.09 KT (L g–1) 0.442
KL (L mg–1) 0.0298 0.032 n 3.190 3.688 BT (J mol–1) 20.29
R2 0.997 0.975 R2 0.925 0.929 R2 0.968
χ2
0.0072 21.33 χ 2
0.0159 60.59 χ2
27.64
SSR 0.0289 85.307 SSR 0.0638 242.38 SSR 110.57
RL 0.0628 0.0588

KC common models, namely pseudo-first-order and pseudo-­

4.5 Data: Data1_B second-order. The plot of pseudo-second-order for KC and
Model: Langmuir linear KR adsorbents at 25°C for 100  ppm CV is shown in Fig. 4.
4.0 Chi^2 = 0.00722 The values of capacities qe and R2 and rate constants k1, k2 for
R^2 = 0.99703
the two models obtained from kinetic plots, are presented
3.5 Q 109.36886 ±2.99726
K 0.02984 ±0.00623 in Table 3 for 100 and 50 ppm CV solutions.
3.0 Our experiments showed that for the concentrations
studied 50 and 100  ppm at 25°C, the pseudo-second-order
2.5 was fitted more than a pseudo-first-order kinetics model as
Ce/qe

indicated by high values of correlation coefficient R2. Also,

2.0
the theoretical capacity qe calculated from pseudo-second-­
1.5 order is close to experimental capacity in many cases. As a
result, the adsorption of CV by various types of date syrup
1.0 residues followed the pseudo-second-order kinetics model.
This suggests that chemical interaction occurred between
0.5
sorbent and adsorbate. Similar results have been reported in
0.0 the literature for the uptake of CV by palm kernel fiber, male
0 100 200 300 400 flowers of the coconut tree and Punica granatum shell [37–39].
Ce
3.5. Adsorption mechanism
Fig. 3. Langmuir linear plots of uptake of CV by KC at 303  K.
(0.1 g adsorbent, 100 ml of 100 ppm CV dye). The experimental adsorption data of CV by KR are fit-
ted to intra-particle diffusion plots to explain the mechanism
increase in temperature due to more dissolution of CV dye responsible for the adsorption process. The obtained intra-
at high temperature (Table S1). particle diffusion constants and correlation coefficients are
summarized in Table S2, [17,31].
All plots are double linear indicating that the mechanism
3.4. Adsorption kinetics
of adsorption occurred in two stages: The first stage was
The kinetics of CV adsorption onto different types of very fast and happened in less than 15  min for all types of
syrup date residues were estimated according to two major the adsorbent. This indicates that the dye diffuses into the
 M.A. Alfrhan et al. / Desalination and Water Treatment 174 (2020) 361–375 367

a) Pseudo second order rate, KC b) Pseudo second order rate, KR

4 5
3.5
3 4
2.5 3
t/qt 2 t/qt
1.5 2
1
y = 0.0127x + 0.5058 1
0.5 y = 0.0163x + 0.5851
0 R² = 0.9987 0 R² = 0.9871
0 100 200 300 0 100 200 300
t ( min) t ( min)

Fig. 4. Pseudo-second-order plots for the adsorption of 100 ml of CV dye (100 ppm) by 0.1 g of (a) KC and (b) KR adsorbents at 25°C.

Table 3
Pseudo-first-order and pseudo-second-order kinetics models parameters for the adsorption of CV 100 and 50 ppm solution (100 ml)
onto 0.1 g of various types of date residue adsorbents at 25°C

CV dye Adsorbent qexp Pseudo-first-order Pseudo-second-order

(ppm) qe (mg g–1) k1 (min–1) R2 qe (mg g–1) k2 (g mg–1 min–1) R2
100 KR 55.02 42.61 0.0140 0.981 61.35 0.00045 0.987
KC 74.92 62.78 0.0080 0.975 78.74 0.00032 0.998
KF 87.83 81.95 0.0092 0.924 88.49 0.00018 0.945
50 KR 34.84 22.22 0.0105 0.945 36.90 0.00084 0.984
KC 47.86 23.99 0.0053 0.899 40.48 0.00102 0.973
KF 43.25 57.74 0.0168 0.837 55.55 0.00030 0.981

external surface of adsorbent pores with strong interaction (Table 4). The decrease of ΔG negative values with an increase
between (CV) and the surface of the adsorbent. The second in temperature suggests that the adsorption process is more
stage is slower than the first due to the decrease in remaining favorable at low temperatures [41]. The overall adsorption
dye concentration. In this rate-limiting step (second stage), of CV onto all adsorbents indicates an exothermic process at
the dye diffuses through the pores of the adsorbent. Both the all temperatures studied due to negative values of ΔH. Low
first and second stages do not pass through the origin which enthalpy (<40  kJ  mol–1) suggests physical adsorption, while
indicates that the adsorption process is not only controlled by higher enthalpy (>40 kJ mol–1) are characteristics for chemi-
intraparticle diffusion [40]. The values of intraparticle diffu- cal adsorption. The obtained ΔS values were negative, which
sion rate constants in the first stage Ki,1 were higher than that reflects increasing order at the solid-solution interface [42].
of the second stage Ki,2 (Table S2). The reason could be pores Similar phenomena were reported by Chakraborty et al. for
blockage so that fewer sites are available for diffusion. adsorption of crystal violet onto NaOH-modified rice husk
(NMRH), and for adsorption of CV onto rice straw modified
3.6. Thermodynamics parameters with citric acid and for pineapple leaf powder [9,43].

The changes in thermodynamics parameters such as

3.7. Activation thermodynamic parameter
entropy (ΔS), enthalpy (ΔH), and Gibbs free energy (ΔG)
for adsorption of CV onto different types of adsorbents The calculated values of activation enthalpy (ΔH*),
were obtained from linear Van’t Hoff plot and the result are activation entropy (ΔS*), activation free energy (ΔG*) and
reported in Table 4, [16–17,28–32]. The plots of lnKe vs. 1/T for activation energy (Ea) for removal of CV by KR, KF and KC
KF and KC are shown in Fig. S3, where Ke is the adsorption are presented in Table 4, [17,31]. Plots of lnk/T vs. 1/T to
equilibrium constant. determine activation parameter and the plots of lnK vs. 1/T
The negative values of ΔG for all types of KR reflects to obtain activation energy for removal of CV by adsorbents
that the adsorption process was feasible and spontaneous KR and KF are shown in Fig. 5 and Fig. S4 respectively, where
368 M.A. Alfrhan et al. / Desalination and Water Treatment 174 (2020) 361–375

Table 4
Thermodynamics and activated thermodynamic parameters for adsorption of 100 ml CV dye (100 ppm) by 0.1 g of different types of
adsorbents at various temperatures

Adsorbent T (K) Ke ΔG (kJ mol–1) ΔH (ΔH*) (KJ mol–1) ΔS (ΔS*) (J mol–1 K–1) ΔG* (kJ mol–1) Ea (kJ mol–1)
KR 293 2.90 –2.80 –64.06 –205.57 102.23 17.59
303 2.29 –1.77 (15.05) (–292.57) 103.70
308 1.27 –0.75 105.16
313 0.89 0.28 106.62
KF 293 19.08 –7.06 –79.07 –241.60 105.56 12.63
303 8.50 –5.86 (10.09) (–320.35) 107.16
308 6.70 –4.65 108.75
313 3.78 –3.44 110.36
KC 293 2.99 –2.36 –14.35 –40.25 106.48 41.14
303 2.27 –2.15 (39.91) (–223.37) 107.59
308 2.09 –1.95 108.71
313 2.04 –1.75 109.83

a) KR b) KF

0.0031 0.0032 0.0033 0.0034 0.0031 0.0032 0.0033 0.0034

-17 -18.5
-18.55
-17.1 -18.6
-17.2 -18.65
y = -1875.1x - 11.334 ln(k/T) -18.7
ln(k/T) -17.3 y = -1259.2x - 14.705
R² = 0.9658 -18.75
-17.4 R² = 0.987
-18.8
-17.5 -18.85
-17.6 -18.9
1/T (K -1) 1/T (K -1)

Fig. 5. Ln(K/T) vs. 1/T plot for the adsorption of 100 ml of CV dye (100 ppm) by 0.1 g of (a) KR and (b) KF.

K is the rate constant. As a result, the positive values of ΔG*

indicate that the adsorption process needs some energy to 3.8. Column adsorption studies
convert reactants onto transition products. Also positive 3.8.1. Breakthrough curve
and low values of (ΔH*) at all temperatures suggest that the
adsorption process is mostly entropy derived for all systems. The column studied was packed with 1  g adsorbent
A negative value of (ΔS*) means that the entropy of reac- dose, and eluted with 200  ppm initial concentration of dye
tants is more than the entropy of activated complex, which concentration at a flow rate of 1 ml min–1. Fig. 6 shows the
reflects that order in adsorption reaction increases during breakthrough curves for two cycles of CV adsorption onto
the formation of an activated complex between the adsor- KF and KC. The column parameters, % removal and capacity
bent and adsorbate and involves associative mechanism [44]. (qe) are calculated for the two cycles of CV from the break-
Ea values obtained for all types of KR are reported in Table 4. through area method as shown (Table 5) [17,30,31]. Fig. S5
At low Ea values in the range between 5 and 40 kJ mol–1 the shows the plot of concentration of dye adsorbed Cad (mg L–1)
adsorption mechanism is controlled by physical adsorption, vs. time (min) of KF and KC for each of cycle 1 and cycle 2,
while for the high value of Ea between 40 and 800 kJ mol–1 from which the area under the breakthrough curve was calcu-
the adsorption mechanism is chemical adsorption [45]. In lated (Table 5). Regeneration for column reuse was achieved
the case of adsorption of CV onto KR and KF adsorbents, with up to 99% efficiency by using dilute HCL 0.3 M.
Ea values were smaller than 40 kJ mol–1 indicating a physical Table 5 shows that the column filled with KF has the high-
mechanism for adsorption. While the mechanism is chemical est adsorption capacity 131.86 mg g–1 for the first cycle and
in the case of KC that column saturation occurred after the passage of 800 ml
 M.A. Alfrhan et al. / Desalination and Water Treatment 174 (2020) 361–375 369

cycle 1 cycle 1
cycle 2 cycle 2
a) KF
1.0 1.0

b) KC
0.8 0.8

0.6 0.6
Ce/Co

Ce/Co
0.4 0.4

0.2 0.2

0.0 0.0

0 200 400 600 800 1000 0 100 200 300 400 500 600 700 800
V(effluent)ml V(effluent)ml

Fig. 6. Breakthrough curve for crystal violet uptake onto (a) KF and (b) KC respectively, (1 g adsorbent dose, 200 ppm initial dye
concentration, flow rate 1 ml min–1).

Table 5
% removal and capacity of column adsorption of CV by KF and KC. (1 g adsorbent dose, 200 ppm initial dye concentration, flow rate
1 ml min–1)

Adsorbent Cycle Area qtotal Mtotal % qe Column saturation

(mg min L–1) (mg) (mg) removal (mg g–1) time (min)
KC Cycle 1 85,303.57 85.30 125 85.30 68.24 625
Cycle 2 62,916.14 62.92 105 62.92 59.92 525
KF Cycle 1 131,857.40 131.86 160 82.41 131.86 800
Cycle 2 98,322.22 98.32 140 70.23 98.32 700

of crystal violet (200 ppm) solution with percent removal of All models fit well with the experimental breakthrough
82.41%. While column study, using KC raw mixture material curves, having high values of R2 and small error function
shows lower adsorption capacity (68.24 mg g–1) for the first (c2 and SSR) (Table 6). The column capacities obtained by
cycle. The exhaustion point of the column for the adsorption Thomas and Yoon-Nelson nonlinear models were closer to
of CV by KC is obtained after the passage of the 625 ml CV the one obtained by the method of the area under the break-
solution. through curve and thus they describe best the behavior of
adsorption of CV dye. While Yan et al. model showed much
3.8.2. Column kinetic model smaller capacity value and so it is less applicable.

In this study, Thomas, Yoon-Nelson and Yan et al. mod-

3.9. Comparison of maximum adsorption capacity with other
els were used to analyze column performance using the
adsorbent material
first cycle of column data for the adsorption CV by KF and
KC [17,31,46]. The nonlinear regression was applied to plot The comparison of adsorption capacities of KR, KF, and
adsorption data according to model equations in order to KC in the present study with other low-cost adsorbents for
describe the behavior of adsorption of CV in a fixed bed col- the removal of crystal violet in batch and column model
umn. For Thomas model, a plot of Ce/C0 vs. time t (min) gave are shown in Table 7 [6,9,13,34,38,41,45,46–52]. The result
the values of Thomas constant and capacity KT and qT, where indicates that KF with the highest capacities can be consid-
Ce (mg L–1) is the concentration of adsorbate in the effluent, ered as a promising adsorbent to remove crystal violet from
C0 (mg L–1) is the initial concentration of the adsorbate in the aqueous solution.
feed solution. Yoon-Nelson plot of Ce/C0 vs. time t gave the
values of Yoon-Nelson constant and capacity KYN and qYN.
4. Conclusion
While from Yan et al. plot of Ce/C0 vs. t, the values of Yan
constant and capacity KY and qY were determined. The col- • Khalas Syrup date manufacture waste residues (SDIR)
umn kinetic parameter results for each model are presented as agricultural waste, is a promising adsorbent for the
in Table 6. Representative Thomas nonlinear model plots for uptake of CV dye from aqueous solution.
the first cycle of adsorption of crystal violet by KF and KC are • The adsorption process of crystal violet shows sig-
shown in Fig. 7. nificant improvement in sorption capacity with
370 M.A. Alfrhan et al. / Desalination and Water Treatment 174 (2020) 361–375

KC
KF
Data: Data1_B Data: Data1_B
Model: Thomas column nonlinear 1.0 Model: Thomas column nonlinear
1.0
Chi^2 = 0.00059 Chi^2 = 0.0011
R^2 = 0.99555 R^2 = 0.99264
0.8
0.8 P1 0.11768±0.00507 P1 0.07073 ±0.00306
P2 136.57739 ±0.42079 P2 89.11112 ±0.68403

0.6
0.6

Ce/Co
Ce/Co

0.4 0.4

0.2 0.2

0.0 0.0

0 200 400 600 800 1000 0 100 200 300 400 500 600 700 800
t(min) t(min)

Fig. 7. Thomas nonlinear model plot for the first cycle of adsorption of crystal violet onto KF and KC, (1 g adsorbent dose, 200 ppm
initial concentration of dye, flow rate 1 ml min–1).

Table 6
Column kinetic parameters for adsorption CV (200 ppm) onto KF and KC with (1 g) packed column. (1 g adsorbent dose, 200 ppm
initial dye concentration, flow rate 1 ml min–1)

Adsorbent Thomas Yoon-Nelson Yan et al.

KT (mL min–1 mg–1) 0.118 KYN (min–1) 0.0235 KY (mL min–1) 8 × 10–5
KF qT (mg g ) –1
136.58 qYN (mg g ) –1
137.11 qY (mg g )
–1
8.54
τ(min) 682.28
R2 0.996 R2 0.996 R2 0.996
χ2 6 × 10–4 χ2 6 × 10–4 χ2 5.0 × 10–4
SSR 0.0187 SSR 0.0187 SSR 0.0159
KC KT (mL min–1 mg–1) 0.0707 KYN (min–1) 0.0142 KY (mL min–1) 3.0 × 10–5
qT (mg g–1) 89.11 qYN (mg g–1) 89.00 qY (mg g–1) 14.24
τ(min) 445.55
R2 0.992 R2 0.992 R2 0.996
χ2 0.0011 χ2 0.0011 χ2 5 × 10–5
SSR 0.0287 SSR 0.0287 SSR 0.0130

pretreated adsorbent with formaldehyde KF and calcium • Thermodynamic study of crystal violet adsorption sug-
chloride KC. gests that the adsorption process is exothermic and spon-
• The adsorbents characteristics were examined by FTIR, taneous due to the negative values of both enthalpy and
SEM, and TGA which confirmed the successful dye free energy change.
adsorption onto different types of SDIR (KR, KF, and KC). • In a fix-bed column study, for uptake of CV by KF and
• In the batch experiment, the adsorption of crystal violet KC date waste residues, Thomas and Yoon-Nelson col-
was found to increase in agitation time and reaches equi- umn kinetics models describe the experimental kinetic
librium at 240  min. However, the adsorption process is data better than Yan et al model based on the values of
favorable at low temperatures. correlation coefficient (R2) and function error values.
• Both Langmuir and Freundlich isothermal models were The calculated high capacity of CV adsorption is close
best fitted to experimental data and perfectly describe the to the value obtained from the breakthrough curve area
adsorption process more than the Temkin model based method.
on the value of correlation coefficient (R2) and function • Comparative study of adsorption capacity of syrup date
error values. manufacture residues and other adsorbent materials for
• The adsorption kinetics followed pseudo-second-order the uptake of CV proves that the highest value of the
which indicates chemisorption. The intraparticle diffu- adsorption capacity occurred with (CF) compared to
sion model is not the sole rate-limiting step. other agricultural waste materials.
 M.A. Alfrhan et al. / Desalination and Water Treatment 174 (2020) 361–375 371

Table 7
Comparison of maximum adsorption capacity of KR, KF and KC with different adsorbents in batch mode and (column) mode

Adsorbent Batch capacity References

(column capacity) (mg g–1)
Treated ginger waste 227.7 [34]
(72.6)
Grapefruit peel 254.16 [6]
Palm kernel fiber 78.9 [38]
NaOH-modified rice husk 44.87 [47]
Tea dust 175.4 [48]
Citric acid modified rice straw 80.91 [9]
(77.185) [41]
Jackfruit leaf powder 43.39 [49]
HCl-modified Citrullus lanatus (61.49) [45]
Rind 104.76 [13]
Citrullus lanatus rind (46.68) [50]
Water hyacinth 12.22 [51]
Date stone 90.89 [52]
KR 89.31 This study
KF 144.49 This study
(136.58)
KC 108.25 This study
(89.11)

• It can be concluded that SDIR (raw and treated) can be [6] A. Saeed, M. Sharif, M. Iqbal, Application potential of grapefruit
used as an available free low-cost preparation and local peel as dye sorbent: kinetics, equilibrium and mechanism of
crystal violet adsorption, J. Hazard. Mater., 179 (2010) 564–572.
alternative for activated carbon to remove crystal violet
[7] G.B. Michaels, D.L. Lewis, Sorption and toxicity of azo and
from wastewater. triphyenylmethane dyes to aquatic microbial populations,
• The prepared modified date residues can be used to Environ. Toxicol. Chem., 4 (2006) 45–50.
remove organic pollutants present in the wastewater. [8] S. Mani, R.N. Bharagava, Exposure to crystal violet, its toxic,
• The availability of cheap date residues and its simple genotoxic and carcinogenic effects on environment and its
degradation and detoxification for environmental safety,
modification as well as the efficient adsorption method
Rev. Environ. Contam. Toxicol., 237 (2016) 71–104.
encourage their applications in industry. [9] S. Chowdhury, S. Chakraborty, P. Das (Saha), Adsorption of
• Prospect is to investigate the treatment of industrial crystal violet from aqueous solution by citric acid modified
wastewater using modified dates residues. rice straw: equilibrium, kinetics, and thermodynamics, Sep. Sci.
Technol., 48 (2013) 1339–1348.
[10] S. Chowdhury, S. Chakraborty, P.D. Saha, Response surface
Acknowledgment optimization of a dynamic dye adsorption process: a case study
of crystal violet adsorption onto NaOH-modified rice husk,
The financial support from the Deanship of Scientific Environ. Sci. Pollut. Res., 20 (2013) 1698–1705.
Research (Project Number 160047) King Faisal University, is [11] S. Chakraborty, S. Chowdhury, P.D. Saha, Adsorption of crystal
greatly acknowledged. violet from aqueous solution onto sugarcane bagasse: central
composite design for optimization of process variables, J. Water
Reuse Desal., 2 (2012) 55–65.
References [12] S. Chakraborty, S. Chowdhury, P.D. Saha, Batch removal
of crystal violet from aqueous solution by H2SO4 modified
[1] V. Bonney, C.H. Browning, Sterilization of the skin and other sugarcane bagasse: equilibrium, kinetic, and thermodynamic
surfaces by a mixture of crystal violet and brilliant green, profile, Sep. Sci. Technol., 47 (2012) 1898–1905.
Br Med J., 1 (1981) 562–563. [13] R. Lakshmipathy, N.C. Sarada, Adsorptive removal of basic
[2] W. Azmi, R.K. Sani, U.C. Banerjee, Biodegradation of tripheny­ cationic dyes from aqueous solution by chemically protonated
lmethane dyes, Enzyme Microb. Technol., 22 (1998) 185–191. watermelon (Citrullus lanatus) rind biomass, Desal. Wat. Treat.,
[3] M.R. Kulkarni, T. Revanth, A. Acharya, P. Bhat, Removal of 52 (2014) 6175–6184.
Crystal Violet dye from aqueous solution using water hyacinth: [14] N. Laskar, U. Kumar, Adsorption of Crystal Violet from
equilibrium, kinetics and thermodynamics study, Resour.-Effic. wastewater by modified Bambusa Tulda, KSCE J. Civ. Eng.,
Technol., 3 (2017) 71–77. 22 (2018) 2755–2763.
[4] M. Iqbal, M.Z. Ahmad, I.A. Bhatti, K. Qureshi, A. Khan, [15] N. Tahir, H.N. Bhatti, M. Iqbal, S. Noreen, Biopolymers
Cytotoxicity reduction of wastewater treated by advanced composites with peanut hull waste biomass and application
oxidation process, Chem. Int., 1 (2015) 53–59. for Crystal Violet adsorption, Int. J. Biol. Macromol., 94 (2017)
[5] A. Mittal, J. Mittal, A. Malviya, D. Kaur, V.K. Gupta, Adsorption 210–220.
of hazardous dye crystal violet from wastewater by waste [16] H.H. Hammud, L. Fayoumi, H. Holail, El-Sayed M.E. Mostafa,
materials, J. Colloid Interface Sci., 343 (2010) 463–473. Biosorption studies of methylene blue by mediterranean algae
372 M.A. Alfrhan et al. / Desalination and Water Treatment 174 (2020) 361–375

carolina and its chemically modified forms. linear and nonlinear [36] C. Kannan, N. Buvaneswari, T. Palvannan, Removal of plant
models’ prediction based on statistical error calculation, Int. J. poisoning dyes by adsorption on Tomato Plant Root and green
Chem., 3 (2011) 147–163. carbon from aqueous solution and its recovery, Desalination,
[17] M. Hanbali, H. Holail, H. Hammud, Remediation of lead by 249 (2009) 1132–1138.
pretreated red algae: adsorption isotherm, kinetic, column [37] S. Senthilkumaar, P. Kalaamani, C.V. Subburaam, Liquid phase
modeling and simulation studies, Green Chem. Lett. Rev., adsorption of Crystal violet onto activated carbons derived
7 (2014) 342–358. from male flowers of coconut tree, J. Hazard. Mater., 136 (2006)
[18] U.K. Garg, M.P. Kaur, V.K. Garg, D. Sud, Removal of nickel(II) 800–808.
from aqueous solution by adsorption on agricultural waste [38] G.O. El-Sayed, Removal of methylene blue and crystal violet
biomass using a response surface methodological approach, from aqueous solutions by palm kernel fiber, Desalination,
Bioresour. Technol., 99 (2008) 1325–1331. 272 (2011) 225–232.
[19] A.L. Cazetta, A.M.M. Vargas, E.M. Nogami, M.H. Kunita, [39] M.B. Silveira, F.A. Pavan, N.F. Gelos, E.C. Lima, S.L.P. Dias,
M.R. Guilherme, A.C. Martins, T.L. Silva, J.C.G. Moraes, Punica granatum shell preparation, characterization, and use for
V.C. Almeida, NaOH-activated carbon of high surface area crystal violet removal from aqueous solution, CLEAN - Soil Air
produced from coconut shell: kinetics and equilibrium studies Water, 42 (2014) 939–946.
from the methylene blue adsorption, Chem. Eng. J., 174 (2011) [40] N.T. Abdel-Ghani, G.A. El-Chaghaby, E.M. Zahran, Penta­
117–125. chlorophenol (PCP) adsorption from aqueous solution by
[20] S. Jain, R.V. Jayaram, Removal of basic dyes from aqueous activated carbons prepared from corn wastes, Int. J. Environ.
solution by low-cost adsorbent: wood apple shell (Feronia Sci. Technol., 12 (2015) 211–222.
acidissima), Desalination, 250 (2010) 921–927. [41] Z.K. Zhou, S.Q. Lin, T.L. Yue, T.-C. Lee, Adsorption of food dyes
[21] Y. Kismir, A.Z. Aroguz, Adsorption characteristics of the from aqueous solution by glutaraldehyde cross-linked magnetic
hazardous dye Brilliant Green on Saklıkent mud, Chem. Eng. J., chitosan nanoparticles, J. Food Eng., 126 (2014) 133–141.
172 (2011) 199–206. [42] C. Varlikli, V. Bekiari, M. Kus, N. Boduroglu, I. Oner, P. Lianos,
[22] L.B.L. Lim, N. Priyantha, C.H. Ing, M.K. Dahri, D.T.B. Tenna­ G. Lyberatos, S. Icli, Adsorption of dyes on Sahara desert sand,
koon, T. Zehra, M. Suklueng, Artocarpus odoratissimus skin as a J. Hazard. Mater., 170 (2009) 27–34.
potential low-cost biosorbent for the removal of methylene blue [43] S. Chakraborty, S. Chowdhury, P.D. Saha, Insight into
and methyl violet 2B, Desal. Wat. Treat., 53 (2015) 1–12. biosorption equilibrium, kinetics and thermodynamics of
[23] J.E. White, W.J. Catallo, B.L. Legendre, Biomass pyrolysis crystal violet onto Ananas comosus (pineapple) leaf powder,
kinetics: a comparative critical review with relevant agricultural Appl. Water Sci., 2 (2012) 135–141.
residue case studies, J. Anal. Appl. Pyrolysis, 91 (2011) 1–33. [44] T. Sismanoglu, A. Ercag, S. Pura, E. Ercag, Kinetics and
[24] S. Ouajai, R.A. Shanks, Composition, structure and thermal isotherms of dazomet adsorption on natural adsorbents, J. Braz.
degradation of hemp cellulose after chemical treatments, Chem. Soc., 15 (2004) 669–675.
Polym. Degrad. Stab., 89 (2005) 327–335. [45] T.S. Anirudhan, P.G. Radhakrishnan, Thermodynamics and
[25] X. Zhang, F. Wang, L.M. Keer, Influence of surface modification kinetics of adsorption of Cu(II) from aqueous solutions onto
on the microstructure and thermo-mechanical properties of a new cation exchanger derived from tamarind fruit shell,
bamboo fibers, Materials (Basel), 8 (2015) 6597–6608. J. Chem. Thermodyn., 40 (2008) 702–709.
[26] R. Ahmad, Studies on adsorption of crystal violet dye from [46] H.H. Hassan, B. El Hamaoui, N.H. Noubani, X.L. Feng,
aqueous solution onto coniferous pinus bark powder (CPBP), Z.-S. Wu, K. Müllen, K. Ayub, Carbon-cobalt nanostructures
J. Hazard. Mater., 171 (2009) 767–773. as an efficient adsorbent of malachite green, Nanosci. Nano­
[27] T.C. Chandra, M.M. Mirna, Y. Sudaryanto, S. Ismadji, Adsorp­ technol.-Asia, 8 (2018) 263–280.
tion of basic dye onto activated carbon prepared from durian [47] S. Chakraborty, S. Chowdhury, P.D. Saha, Adsorption of Crystal
shell: studies of adsorption equilibrium and kinetics, Chem. Violet from aqueous solution onto NaOH-modified rice husk,
Eng. J., 127 (2007) 121–129. Carbohydr. Polym., 86 (2011) 1533–1541.
[28] M. Alshabanat, G. Alsenani, R. Almufarij, Removal of crystal [48] M.M.R. Khan, M.W. Rahman, H.R. Ong, A.B. Ismail, C.K. Cheng,
violet dye from aqueous solutions onto date palm fiber by Tea dust as a potential low-cost adsorbent for the removal
adsorption technique, J. Chem., (2013) 1–6, http://dx.doi. of crystal violet from aqueous solution, Desal. Wat. Treat.,
org/10.1155/2013/210239. 57 (2016) 14728–14738.
[29] H.H. Hammud, I. Abbas, D. Al-khalili, Kinetics and thermo­ [49] P.D. Saha, S. Chakraborty, S. Chowdhury, Batch and continuous
dynamics of chromate and phosphate uptake by polypyrrole: (fixed-bed column) biosorption of crystal violet by Artocarpus
batch and column studies, J. Inclusion Phenom. Macrocyclic heterophyllus (jackfruit) leaf powder, Colloids Surf., B, 92 (2012)
Chem., 82 (2015) 395–405. 262–270.
[30] H.H. Hammud, M.M. Chahine, B. El Hamaoui, Y. Hanifehpour, [50] K.S. Bharathi, S.P.T. Ramesh, Fixed-bed column studies on
Lead uptake by new silica‐carbon nanoparticles, Eur. J. Chem., biosorption of crystal violet from aqueous solution by Citrullus
4 (2013) 432‐440. lanatus rind and Cyperus rotundus, Appl. Water Sci., 3 (2013)
[31] H.H. Hammud, A. Shmait, N. Hourani, Removal of malachite 673–687.
green from water using hydrothermally carbonized pine [51] K. Murali, P. Arunkumar, J. Kanmani, S. Kurunthasala Prabu,
needles, RSC Adv., 5 (2015) 7909–7920. N. Jayaganesh, Removal of Crystal violet dye using water
[32] I.I. Abbas, H.H. Hammud, H. Shamsaldeen, Calix[4]pyrrole hyacinth, Int. J. Eng. Res. Modern Educ., Special Issue, (2017)
macrocycle: extraction of Fluoride anions from aqueous media, 139–141.
Eur. J. Chem., 3 (2012) 156–162. [52] N. El Messaoudi, M. El Khomri, S. Bentahar, A. Dbik,
[33] X.-J. Xiong, X.-J. Meng T.-L. Zheng, Biosorption of C.I. Direct A. Lacherai, Removal of crystal violet by biosorption onto date
Blue 199 from aqueous solution by nonviable Aspergillus niger, stones, Sci. Study Res. Chem. Chem. Eng. Biotechnol. Food Ind.,
J. Hazard. Mater., 175 (2010) 241–246. 17 (2016) 151–167.
[34] R. Kumar, R. Ahmad, Biosorption of hazardous crystal violet
dye from aqueous solution onto treated ginger waste (TGW),
Desalination, 265 (2011) 112–118.
[35] A. Sulyman, M. Namieśnik, A. Gierak, Adsorptive removal of
aqueous phase crystal violet dye by low-cost activated carbon
obtained from Date palm (L.) dead leaflets, Inżynieria i Ochrona
Środowiska, 19 (2016) 611–631.
 M.A. Alfrhan et al. / Desalination and Water Treatment 174 (2020) 361–375 373

Supplementary information

FTIR of Khalas date resiue KF before and KF* after CV dye adsorption
120

KF
100

KF*
80

60

40

20

0
0 500 1000 1500 2000 2500 3000 3500 4000 4500

KF residue KF residue aer adsorpon of CV dye

Fig. S1. FTIR spectrum of formaldehyde modified residues KF before and KF* after adsorption of CV dye.

KC
110

100

90 Data: Data1_B
Model: Temkin nonlinear
80 Chi^2 = 27.64439
R^2 = 0.968
70 Kt 0.44203 ±0.16319
qe

b 20.29089 ±1.84454
60

50

40

30

0 100 200 300 400

Ce
Fig. S2. Temkin nonlinear plots for the uptake of crystal violet 100 ml
(50–500 ppm) by 0.1 g of CV dye by KC at 303 K.
374 M.A. Alfrhan et al. / Desalination and Water Treatment 174 (2020) 361–375

a) KF b) KC
y = 9510.5x - 29.061 y = 1726.5x - 4.8413
R² = 0.9622 R² = 0.9541
3.5 1.2
lnKe 3 lnKe 1
2.5
0.8
2
1.5 0.6
1 0.4
0.5 0.2
0
0
0.0031 0.0032 0.0033 0.0034
0.0031 0.0033 0.0035
1/T(K -1)
1/T(K -1)

Fig. S3. LnKe vs. 1/T Plots for the adsorption of CV dye (100 ml and 100 ppm) onto KF and KC.

a) KR b) KF

0.0031 0.0032 0.0033 0.0034 0.0031 0.0032 0.0033 0.0034

-11.2 -12.85
-11.3 -12.9
-11.4 -12.95
y = -2115.6x - 4.7095 y = -1519.4x - 8.049
-11.5 -13
ln(k) R² = 0.9742 ln(k) R² = 0.9918
-11.6 -13.05
-11.7 -13.1
-11.8 -13.15
-11.9 -13.2
1/T (K -1) 1/T (K -1)

Fig. S4. LnK vs. 1/T plot for the adsorption of CV dye (100 ml and 100 ppm) by 0.1 g (a) KR and (b) KF.

200 200

(KC) cycle1 (KC) cycle 2

150 150
Cad(mg/L)

Cad(mg/L)

100 100

50 50

0 0
100 200 300 400 500 600 700 100 200 300 400 500 600
Time(min) Time(min)

Fig. S5. Plots of Cad against time (min) for KC of cycle 1 and cycle 2. (1 g adsorbent dose, 200 ppm initial dye concentration, flow rate
1 ml min–1).
 M.A. Alfrhan et al. / Desalination and Water Treatment 174 (2020) 361–375 375

Table S1
Nonlinear isotherm models for the adsorption of 100 ml of crystal violet (50–500 ppm) by 0.1 g of KR modified with formaldehyde
KF at different temperatures

Langmuir Freundlich Temkin

T (K) qm K R2 KF n R2 KT BT R2

298 151.28 0.083 0.921 40.10 4.28 0.984 2.79609 21.754 0.977
χ2 SSR R χ2 SSR R χ2 SSR R
223.79 671.38 0.960 18.368 91.84 0.994 38.530 192.65 0.988
303 qm K R2 KF n R2 KT BT R2
144.49 0.086 0.964 35.256 4.12 0.955 1.56988 22.412 0.9518
χ2 SSR R χ2 SSR R χ2 SSR R
90.65 271.96 0.981 83.07 332.28 0.977 90.1608 360.64 0.975
308 qm K R2 KF n R2 KT BT R2
142.12 0.046 0.964 28.36 3.709 0.911 0.83733 23.459 0.9124
χ2 SSR R χ2 SSR R χ2 SSR R
83.81 251.45 0.982 158.85 635.43 0.954 157.482 629.92 0.9552
313 qm K R2 KF n R2 KT BT R2
114.28 0.0733 0.931 36.78 5.139 0.828 2.10757 17.357 0.873
χ2 SSR R χ2 SSR R χ2 SSR R
65.04 260.16 0.964 161.98 647.92 0.910 119.046 476.18 0.9348

Table S2
Intraparticle diffusion rate constants and parameters for the adsorption of CV 100 ppm solution (100 ml) by 0.1 g KR, KF, and KC at
25°C

Adsorbent Ki,1 (mg (g–1 min–1/2)) I1 (mg g–1) R2 Ki,2 (mg (g–1 min–1/2)) I2 (mg g–1) R2

KR 2.65 15.17 0.965 0.0518 53.05 1
KC 3.57 16.61 0.987 0.2238 66.27 1
KF 4.79 4.23 0.973 0.337 75.05 0.999