8 - Una Revisión de Adsorbentes Derivados de Residuos de La Industria Azucarera para La Eliminación de Contaminantes en Agua y Aguas Residuales
8 - Una Revisión de Adsorbentes Derivados de Residuos de La Industria Azucarera para La Eliminación de Contaminantes en Agua y Aguas Residuales
PII: S0167-7322(17)31331-4
DOI: doi: 10.1016/j.molliq.2017.05.063
Reference: MOLLIQ 7355
To appear in: Journal of Molecular Liquids
Received date: 28 March 2017
Revised date: 14 May 2017
Accepted date: 15 May 2017
Please cite this article as: Ioannis Anastopoulos, Amit Bhatnagar, Bassim H. Hameed,
Yong Sik Ok, Michalis Omirou , A review on waste-derived adsorbents from sugar
industry for pollutant removal in water and wastewater, Journal of Molecular Liquids
(2017), doi: 10.1016/j.molliq.2017.05.063
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a
Department of Agrobiotechnology, Agricultural Research Institute, P.O. Box 22016,
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1516, Nicosia, Cyprus
b
Department of Environmental and Biological Sciences, University of Eastern
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Finland, P.O. Box 1627, FI-70211, Kuopio, Finland
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c
School of Chemical Engineering, Engineering Campus, Universiti Sains Malaysia,
d
School of Natural Resources and Environmental Science & Korea Biochar Research
Corresponding author. Tel.: +357-22403151
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[email protected](I. Anastopoulos)
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Abstract
Sugar industry generates a significant amount of by-products (such as sugar beet pulp
(SBP), sugar bagasse (SB)) and their handling and management is a matter of great
concern. Among their uses such as fuel and fertilizer, the valorization of biowastes
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from sugar industry as adsorbents for the removal of various aquatic pollutants
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presents promising features in terms of cost reduction for waste disposal and
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environmental protection. This review article deals with the use of sugar waste based
materials used as adsorbents in water treatment. For this purpose, isotherms, kinetics,
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desorption and thermodynamic information are thoroughly presented. Moreover,
many parameters which control the adsorption process, such as the effect of initial
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concentration, initial solution pH, contact time, temperature and adsorbent's dose, are
also discussed in detailed. The performance of the adsorbents largely depends on the
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greatly enhance the removal efficiency with favorable kinetics and adsorption
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mechanism.
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Content:
Page
1. Introduction ……………………………………………………………5
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2.1 Raw sugar wastes ……………………………………………………..7
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2.3 Sugar waste based adsorbents ………………………………………11
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3. Sugar wastes for dyes removal …………………………………………13
References ………………………………………………………………….36
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Abbreviation list
MB Methylene blue
EB Erythrosin B
MG Malachite green
AO7 Acid orange 7
CPBr Cetylpyridinium bromide
OR2 Orange II
CR Congo red
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MR Methyl red
RBB Remazol black B
BB3 Basic blue 3
RO16 Reactive orange 16
CRR195 Chemazol reactive red 195
BV16 Basic violet 16
RR2 Reactive red 2
AR1 Acid red 1
SA Safranin
DW Distilled water
SBP Sugar beet pulp
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SCB Sugarcane bagasse
COD Chemical oxygen demand
FTIR Fourier transform infrared spectroscopy
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BET Brunauer,Emmett and Teller
Ea Activation energy
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C-SCB Carbonaceous bagasse
CPBr Cetylpyridinium bromide
F-SCB) Formaldehyde- Sugarcane bagasse
S-SCB Sulphuric acid-SCB
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PAC Commercial activated carbon
QSCB Quartenized sugarcane bagasse
DSBPC Dehydrated sugar beet pulp carbon
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F Freundlich
Ps1 Pseudo-first-order
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Ps2 Pseudo-second-order
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1. Introduction
Water pollution due to industrial, agricultural and domestic activities has caused
treatment technologies have been developed during the last few decades [2]. Among
them, adsorption still remains the most favorable process for removing pollutants
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from water and wastewater due to its simplicity to design, easiness to operate and low
cost [3].
Activated carbon has been used for this purpose since long, but focus has
such as rice husk, wheat straw, coffee waste, coconut wastes, peanut hull, fruits and
vegetable peels, sludges, steel slag, red mud, sugarcane bagasse etc. [4-13].
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Various industries produce huge amounts of wastes which create disposal
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problems as well as environmental pollution in many ways (air, soil and water). Sugar
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industry is one such industries generating large amounts of wastes [14, 15]. Around
160 million tons of sugar are produced annually from more than 123 sugar-producing
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countries with Brazil, India, China, Thailand and Pakistan as top five producers. A
consists elevated levels of suspended solids, organic matter, effluent, sludge, press
Bagasse and filter cake are two main types of solid wastes generated by
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sugarcane industry [17, 18]. The solid residual material, left after the juice is extracted
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33% residue of the total cane crushed [17, 18]. It has a calorific value of about 1920
kcal/kg [17, 18] and is mainly used as fuel in boilers for steam generation. For each
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10 tons of sugarcane crushed, a sugar factory produces nearly 3 tons of wet bagasse.
Bagasse fly ash is produced when bagasse is burned to generate energy and steam for
power. The precipitate in the form of sludge slurry after filtration is termed as filter
Press mud is a residue of sugarcane juice filtration process [19]. It contains all
non-sucrose impurities along with CaCO3 precipitate and sulphate. Press mud from
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potassium, etc., and therefore used as a fertilizer. The press mud from double
carbonation process is used for land filling [20]. Molasses is a by-product left over
from the process of crystallization of sugar from the sugarcane juice [21].
wastewater, emissions and solid wastes. The massive quantities of plant matter and
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sludge washed from mills are decomposed in freshwater bodies, absorbing available
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oxygen and leading to massive fish kills [22]. In addition, mills release flue gases,
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soot, ash, ammonia and other substances during processing. If all the by-products of
sugar industry can be used for converting into value-added products, it will minimize
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the pollution load to a large extent. Sugar industry wastes are, therefore, a promising
wastewater. This paper presents the recent advances in the utilization of sugar
aquatic pollutants.
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Heavy metals are recognized as one of the most toxic groups which reach in
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food chain through the disposal of wastes to water receptors or land. Heavy metals are
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taxed in causing toxic effects, cancer and diseases because they cannot be degraded
[23-25]. The most important factors which affect their mobility are pH, sorbent
nature, presence and concentration of organic and inorganic ligands [26]. The
maximum adsorption monolayer capacity, best isotherm and kinetic models are
tabulated in Table 1.
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The adsorption of Mn2+ by sugar beet pulp (SBP) and sugarcane bagasse (SCB)
from aqueous solution was examined by Ahmed et al. [27]. Optimum adsorption
conditions for SCB was obtained at pH 6, 1.5 g and equilibrium was reached after 150
min, while for BP optimum adsorption conditions were recorded at pH 6 and 1 g and
the equilibrium time was attained after 90 min. FTIR spectra before and after Mn2+
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adsorption were used to determine the functional groups which participated in
adsorption process. For both SCB and SBP, it was found that oxygen containing
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functional groups vis, methoxy –OCH3, carboxy–COOH and phenolic –OH groups
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were affected after removal process. Intra particle diffusion was found to involve in
uptake process but it was not the only rate limiting step.
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Moubarik et al. [28] examined the use of SCB for the uptake of Cd2+. Highest
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removal was noticed at pH 7 and at 25 oC and the equilibrium was reached in 25 min.
physisorption. The adsorption percentage was found to increase from 87 to 96% as the
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SCB was also used as adsorbent for the removal of Cd2+ from aqueous solutions
[29]. Maximum adsorption was achieved at 150 rpm of agitation rate and at pH 5 – 7.
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Adsorption was noticed to be fast and equilibrium was reached after about 90 min of
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contact time. Kinetic studies showed that pore diffusion was not the only rate-limiting
step. Rosmi et al. [30] also concluded that maximum adsorption percentage (55%) of
Cd2+ by SCB was achieved at pH 7, with 120 min of contact time and 1 g of adsorbent
dosage.
Pehlivan et al. [31] studied the adsorption of Pb2+ and Cd2+ by SBP. The pH
was found to control the uptake process and maximum adsorption was found at pH
5.3 and 5, for Cd2+ and Pb2+, respectively. Equilibrium time was attained after 70 min
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for both metals and the increase of adsorbent dose from 0.1 g to 1 g caused an
increment of removal efficiency from 57 to 72% for Cd2+ and from 65 to 71% for
Pb2+, respectively. The presence of 0.1 M NaNO3 had no significant effect on Pb2+
and Cd2+ removal, while increasing the ionic strength over 0.1 M NaNO3, a reduction
Batch equilibrium studies were carried out in order to test the uptake of Cu2+ by
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dried SBP [32]. The increase in pH from 2 to 4 was found to positively affect the
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adsorption process and the removal efficiency was raised from to 10.8 to 24.6 mg g-1.
At higher pH values such as 4.5 and 5, a significant decrease of Cu2+ uptake was
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noticed due to the plausible precipitation of Cu2+ as insoluble Cu(OH)2. The increase
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in temperature from 25 to 45 oC had negative effect on Cu2+ adsorption that resulted
in the decrease of the amount adsorbed from 24.6 to 12.3 mg g-1. The external mass
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transfer, intra particle diffusion and sorption process were potential rate controlling-
steps indicated the complexity of the adsorption mechanism. The activation energy of
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SCB and its modified forms (NaOH-SCB and HCl-SCB) were used as
promising adsorbents for the removal of Hg1+ from aqueous solution [33]. Raw
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adsorbents. The highest removal of 97.58% was noticed at pH 4, while for pH values
higher than 4, a decrease was observed due to the potential precipitation of mercury
efficiency in the first minutes but at equilibrium time negligible changes were
performed.
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SCB was treated with 0.1 M oxalic acid in order to use as adsorbent for the
removal of Cu2+ from water [34]. Optimum adsorption conditions were obtained at
pH 2.0 and at 100 min of contact time. Compared to raw SCB, the modified adsorbent
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mg g-1 vs 0.556 mg g-1). Thermodynamic parameters showed the spontaneity and
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endothermicity of adsorption process as well as the positive values of entropy change
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indicated the high degree of randomness at the solid/solution interface.
SBP treated with NaOH and citric acid was also examined for Cu2+ removal
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[35]. Compared with untreated sugar beet pulp, the modified adsorbent had higher
cation exchange capacity (3.21 meq g-1 vs 0.86 meq g-1), suggested higher cation
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swelling capacity and COD values than the untreated SPB. The mean free energy of
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adsorption estimated from Dubinin-Radushkevich and the Polanyi potential was in the
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range 10.91 – 11.95 kJ mol-1 of 25 – 55 oC, suggesting that the ion exchange
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mechanism controlled the adsorption process. Negative values of ΔG0 and ΔH0
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Jiang et al. [36] tested the use of SCB treated with acrylonitrile and
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hydroxylamine with the aim to enhance the ability to adsorb Cu2+ from wastewater.
affected positively the Cu2+ uptake while the raise of temperature from 30 to 60 oC
had negative effect on adsorption capacity (decrease from 101.01 to 59.28 mg g-1).
SCB was pretreated by sulphuric acid and it investigated to adsorb Pb2+ [37].
Potentiometric titrations showed two different types of sites present on adsorbent that
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may be correspond to carboxyl and amine groups. Equilibrium sorption data were
better fitted to Langmuir model than the Freundlich model. Compared to untreated
material, the modified adsorbent had higher adsorption capacity (7.297 mg g-1 vs
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sugarcane bagasse rind beads and SCBPB-sugarcane bagasse pith beads) [38].
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Compared to native adsorbents (SCBR-sugarcane bagasse rind, SCBP-sugarcane
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bagasse pith), immobilized adsorbents showed higher adsorption capability. The pH
was found to control the adsorption process and that maximum adsorption for Cr3+
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and Cr6+ was marked at pH 2 and 5, respectively. Highest uptake capacity was noticed
at 0.1 g of adsorbent dose, while a decreasing trend was appeared at higher adsorbent
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adsorbents in tannery wastewaters was evaluated and the results showed that at
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conditions: pH 2, 0.1 adsorbent dose and 240 min of contact time. The maximum
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chromium adsorption was found as: SCBR (384 mg g-1, 68%), SCBRB (393 mg g-1,
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70.5%), SCBP (404 mg g-1, 72%) and SCBPB (411 mg g-1, 73.5%).
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acrylamide as a crosslinker was examined for the removal of Cu2+, Pb2+ and Cd2+
from aqueous solutions [39]. FTIR spectra before and after adsorption showed that –
COO– and –NH2 participate in adsorption process. The adsorption equilibrium was
reached in 60 min, 90 min and 180 min for Pb2+, Cd2+ and Cu2+, respectively. The
g-1 for Cu2+, 1 to 232 mg g-1 for Cd2+ and from 36 to 246 mg g-1 for Pb2+. Desorption
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studies were achieved by using 1 M HCl and after five adsorption/desorption cycles,
the desorption rates were 95%, 96% and 92% for Pb2+, Cd2+ and Cu2+, respectively.
Iron (III)-impregnated sorbent prepared from SCB was tested for Cr6+ removal
by Zhu et al. [40]. At an adsorbent dose of 300 mg/50 mL, an increase of initial
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chromium (VI) concentration from 25 to 130 mg/L enhanced the amount adsorbed
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from 4.15 to 12.20 mg g-1, from 4.16 to 12.50 mg g-1, and from 4.16 to 13.72 mg g-1 at
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20 °C, 30 °C and 40 °C, respectively. Whereas, a negative effect on adsorption
Activated carbon fabricated from SCB was also examined for the removal of
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Cr6+ [41]. The adsorption was found to decrease from 89.41 to 45.82% with the raise
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affect the uptake efficiency (from 61.4 to 89.4%). Based on the thermodynamic
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Activated carbons obtained from SBP impregnated with phosphoric acid were
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synthesized and examined for Cd2+ uptake [42]. The carbonization process was
carried out by heating the phosphoric acid-treated samples in a fixed bed at different
temperatures (300, 400 and 500 oC). The maximum adsorption percentage was 90.6%,
93.4% and 95.8% at initial pH 6.3 for activated carbons obtained at 300, 400 and 500
o
C, respectively. Adsorption equilibrium was reached after 60 min for all tested
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Ozer and Tumen [43] also examined the use of carbons from SBP which was
carbonized at different temperatures (300, 400 and 500 oC) for the Cu2+ removal. The
optimum pH was observed at pH 5.5 and the equilibrium time was achieved in 120
min whereas increase in adsorbent dosage lead to the increment of the removal up to
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maximum value and then declined. An optimum dosage of 5 g L-1 was obtained with
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maximum adsorption capacities of 9.06, 10.48 and 12.20 mg g-1 for carbons
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Biochar fabricated from SCB was used to adsorb Pb2+ from aqueous solutions
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[44]. The biochar has BET surface area of 92.30 m2 g-1, 12.21% ash content and pH
9.63, probably due to high content of alkali metals such as Ca2+ and Mg2+. The
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maximum removal was observed at pH 5 and 25 oC. The uptake of Pb2+ resemble to
have endothermic nature as the adsorption was not favored at low temperatures. The
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that 1 M HNO3 was ample to regenerate the biochar but the removal efficiency was
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decreased due to the fact that a loss of biomass was noticed by using 1 M HNO3.
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Pectin extracted from SBP was prepared by Ma et al. [45] for the removal of
Hg2+. The adsorption was quick in the first 10 min and attaining equilibrium within 40
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up to 12, the amount of Hg2+ removal decreased. In addition, there was a negligible
Palin et al. [46] utilized SCB, in natural (Nat), colonized by Pleurotus ostreatus
(U12-4), and colonized by Ganoderma lucidum (U12-6) for Pb2+ removal. The points
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of zero charge was found to be 4.6 for residue only with the bagasse, 4.0 for the
residues colonized by P. ostreatus U2-11 and P. ostreatus U12-4, 3.8 for the residue
colonized by G. lucidum, and 3.6 for the residue colonized by L. edodes. For all the
adsorbents, maximum adsorption was found at pH 5 (pH studied range 2 – 5). The
equilibrium was reached in 20 min and the residues colonized with P. ostreatus U2-
11, P. ostreatus U12-4, and G. lucidum showed higher adsorptive capacities than
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(Nat). The value of Gibbs free energy was found to be negative indicating the
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spontaneity of adsorption.
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3. Sugar wastes for dyes removal
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Dyes are an important class of pollutants which came are large amounts from textile,
dyeing, paper and pulp, tannery and paint industries [47] . The main use of dyes is to
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modify the color characteristics of different substrates such paper, fabric, leather and
others [48]. It is already demonstrated that dyes largely affect the photosynthetic
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activity [49]. Moreover, many dyes are toxic and even carcinogenic thus affecting the
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aquatic biota and human health [50]. The maximum adsorption monolayer capacity,
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SCB washed with tap water at least 4 to 5 times, soaked in distilled water for 48
h, dried for 24 h at 100 oC and was examined for Erythrosin B (EB) and methylene
blue (MB) removal using batch mode [51]. Adsorption was maximum at pH 9 and 7-
9, for MB and EB, respectively. Regarding contact time (studied range 10 – 180 min),
temperature from 35 to 55 oC was found to affect differently the uptake of dyes; the
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EB and MB was spontaneous and endothermic with physical nature. The adsorption
ability of SCB to sequestrate MB from aqueous solution was assessed [52]. The
maximum dye uptake capacity for SCB was obtained as 108.67 mg g-1.
Malekbala et al. [53] examined the removal of MB and safranin (SA) by SBP
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from aqueous solution. The increase of adsorbent dose from 0.05 to 0.5 g led to an
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increment of adsorption capacity from 34% to 88% and from 26% to 89%, for MB
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and SA, respectively. Highest adsorption was occurred at pH 10 for both dyes due to
the fact that at low pH values there are repulsive forces between the positively
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charged adsorbent surface and positively charged dyes. Adsorption equilibrium was
reached after 210 min. Desorption studies were carried out using different HCl
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concentrations (0.1, 0.5 and 1 N) and the best desorption amount was observed with
g-1).
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The adsorption of congo red (CR) by ball-milled SCB was studied [54]. The
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pHpzc (point of zero charge) was estimated to be 5 and the raise of pH from 5 to 10
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removal was increased from 11.3% to 98.3% with the increment of adsorbent dosage
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from 1 g L-1 to 20 g L-1. FTIR spectra before and after adsorption demonstrated the
interaction between the carboxyl and hydroxyl groups of the adsorbent and CR
interface.
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The use of SCB to remove malachite green (MG) dye was examined by Sharma
and Nandi [55]. External mass transfer (earlier stages) and intraparticle diffusion
(later stages) were found to control the uptake of dye. The adsorption process was
interface. Based on Boyd model, the external mass transfer was the slowest step
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The ability of SBP to capture basic violet 16 (BV16) dye was assessed by
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Harifi-Mood et al. [56]. Batch experiments were carried out and the results showed
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that the increase of pH from 2 to 13 had negligible effect in the amount removed (only
a smooth increase was noticed after pH 6). Maximum removal of 85.2% was noticed
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using 10 g L-1 of adsorbent dosage. The surface adsorption, bulk diffusion and intra
in the amount adsorbed. The Gibbs free energy was estimated to be negative
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confirming the spontaneity of adsorption process. Fast uptake efficiency was achieved
during initial stage of the removal process and equilibrium was attained in at
raw SB.
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gave the best fit. Compared to raw SCB, the C-SCB showed about 89% dye removal,
possibly due its higher surface area. The adsorption was spontaneous, exothermic
Modified SCB was also examined for MG adsorption [59]. Maximum removal
of 81% was notice at pH 8 (pH studied range 3 – 9) and after 30 min of contact time,
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respectively while optimum adsorption was obtained at 0.6 g adsorbent dose. The
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estimated mean adsorption energy was < 8 kJ mol-1 indicated the physical nature of
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the process.
The adsorption of acid orange 7 (AO7) dye from aqueous solution by SCB and
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cetylpyridinium bromide (CPBr) modified SCB was tested [60]. The pretreated SCB
was modified with three different concentrations of CPBr i.e. 0.1, 1.0, and 4.0 mM,
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giving SCBC1, SCBC2 and SCBC3 adsorbents. The maximum adsorption capacity
followed the sequence in the order: SCBC3 > SCBC2 > SCBC1 > SCB. The pH was
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found to control the removal process and the highest removal occurred at pH 2 and 7
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Raw SCB treated with propionic acid and examined for the removal of MB and
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orange II (OR2) [61]. Maximum adsorption occurred at pH 3-11 and 2, for MB and
OR2 respectively. The increase of adsorbent dose from 0.2 g/50 mL to 2 g/50 mL was
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found to increase the removal percentage. In case of OR2 the effect of particle size
(0.25 – 1 mm particle size range) had negative uptake results. Compared to OR2, MB
adsorbed faster and for both dyes the equilibrium time was achieved after 60 min.
The removal of MB by raw and treated via CaCl2 and NaOH SCB was also
examined [62]. In case of raw SCB, at higher tested concentration, adsorption was
reached plateau in 15 min, while at lowest tested concentration of 0.833 g L-1, 30 min
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was needed to equilibrate. At the intermediate pH, approximately 4 < pH < 8, the
NaOH-SCB gave the highest uptake efficiency. One possible explanation was
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SCB (abbreviated as S-SCB) were fabricated and used to adsorb methyl red [63]. For
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comparison reason, a commercial activated carbon (PAC) was also tested for the same
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purpose. The pH between 7 to 10 was found to favor the MR removal for modified
SCBs while using activated carbon the adsorption was constant for all the pH range.
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The adsorption efficiency followed the order: PAC>S-SCB>F-SCB.
(BB3) and reactive orange 16 (RO16) in single and double dye solution [64]. The
adsorption of BB3 and RO16 was found to enhance at basic (optimum at pH=10) and
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indicated that pseudo-second-order kinetic model and Freundlich isotherm model had
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the best fit to the experimental data. The uptake of BBE was enhanced by raising the
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adsorptive ability to remove reactive red 2 (RR2) [65]. Compared to raw SBP, the
modified SBP exhibited better removal efficiency in the studied pH range (2 – 10)
min and Weber-Morris model showed that intra particle diffusion was involved in
adsorption mechanism but it was not the only rate-limiting step. The mean energy of
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examined the adsorption of acid red 1 (AR1) by quaternary ammonium SBP. At the
optimum pH 2, the equilibrium was attained within 30 min. The raise of temperature
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g-1, respectively. The adsorptive ability of modified SPB in real wastewater (spiked
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with 100 mg L-1 AR1) lead to 93.45% biosorption efficiency demonstrating that there
was no matrix effect. Activation energy (Ea) was estimated to be 22.82 kJ mol-1
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entailed chemisorption mechanism.
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3.3 Sugar waste based adsorbents
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Reticulated formic lignin (RFL) from SCB was used for the uptake of MB [67].
acetate aqueous buffer), 50 oC and 0.1 ionic strength and 12 h of equilibrium time.
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Dursun et al. [68] prepared carbon from SBP to adsorb the remazol black B dye.
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obtained as the temperature increased from 25 to 50 oC. Large amount of dye was
removed in 60 min and the equilibrium time was established in 180 min. The
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[69]. The optimal conditions to fabricate the activated carbon were: liquid-to-solid
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ratio of 5, temperature of 450 °C and phosphoric acid concentration of 3 mol L-1. BET
surface area was estimated to be 1029.31 m2 g-1 and 100 min were found sufficient to
achieve the equilibrium phase. Film diffusion was found to govern the adsorption
process and the intraparticle diffusion was not only the rate-limiting step.
Dehydrated sugar beet pulp carbon (DSBPC) was produced in order to explore
its efficiency to remove Chemazol reactive red 195 CRR195 dye [70]. The pH was
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found to control the adsorption process and maximum removal of CRR195 was
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noticed at pH 1. The raise of temperate from 25 to 50 oC enhanced the adsorption
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capacity due to increase in the number of active sites, porosity and total pore volume
of the adsorbent. Regarding the mechanism of adsorption, both external mass transfer
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and intra-particle diffusion participated in removal process. Thermodynamic study
nature.
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Sugar wastes were also applied for the removal of other pollutants such as nitrate,
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phosphate, fluoride, phenol and COD. Τhe presence of phosphate and nitrate in the
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[72]. Furthermore, high nitrate concentration in drinking water can lead a potential
risk to animal and human health. Excessive level of nitrate in drinking water can
conditions [73]. Modified SCB was also used to adsorb phosphate ions from aqueous
media [74, 75]. Hena et al. [74] reported that the adsorption was found to increase
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significantly from 54.1% to 95.2% when the adsorbent dosage raised from 0.5 to 2 g
Carvalho et al. [75] compared the ability of raw SCB fibres, SCB fibres doped with
Fe2+ ions, carboxymethylated SCB fibres, carboxymethylated SCB fibres doped with
Fe2+ ions, to adsorb phosphate. They concluded that carboxymethylated SCB fibres
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doped with Fe2+ ions exhibited the highest adsorption capability. The adsorption of
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nitrate ions from modified SCB was examined [76]. The increase of initial nitrate
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1.57 mg g-1. The temperature was found to affect the adsorption efficiency. More
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specifically, the removal was enhanced at low temperature (25 oC), whereas with
with 1.5 mg/L as the maximum permissible limit as recommended by World Health
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can be toxic causing dental fluorosis, teeth mottling, skeletal fluorosis and
deformation of bones in children as well as in adults [78, 79]. Singh et al. [80] used
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the SCB to remove fluoride ion from water. Optimum adsorption conditions were
found as 1 g L-1 of adsorbent dosage and pH 5.4. The adsorption capacity was
carried out by changing the pH levels (2 – 12) and the results showed low desorption
potential (3 – 4 %).
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and incriminated for their toxic and carcinogenic effects for aquatic and human being,
respectively. Phenol is very soluble in water, oils, carbon disulfide and numerous
organic solvents [81]. For the aforementioned reasons, the removal of phenol from
wastewater before discharge into water bodied is necessary [82].The toxicity level for
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fish is around 9 to 25 mg/l while that for human being ranges 10-24 mg/l. lethal blood
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concentration of phenol is around 150-mg/100 mL [83].The Environmental Protection
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Agency (EPA) calls for lowering phenol content in the wastewater to less than 1 mg
mL-1 [84]. Activated carbon prepared by SCB [85] and carbonized SBP [86] were
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used to sequestrate phenol ions from aqueous solution. Dursun et al. [86] mentioned
that maximum adsorption was at pH 6 and at 60 oC. Equilibrium was attained in 120
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min for all studied temperatures. Akl et al. [85] concluded that highest adsorption was
observed at pH 7.5 – 8 and more than 90% of phenol was removed within 15 min. An
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increment of uptake capacity was occurred with the raise of temperature from 17 to 55
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C. Kinetic results showed that intra particle diffusion was not the only rate
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controlling step.
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concentrations. COD and BOD reflect the high organic content of wastewater [87].
COD is a measure of the oxygen equivalent of the organic matter in a water sample
Higher COD levels mean that there is a greater amount of oxidizable organic material
dissolved oxygen can lead to anaerobic conditions, which are harmful to higher
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aquatic organisms [90]. Lakdawala and Patel [91] studied the use of bagasse fly ash
to remove COD from wastewater. The bagasse fly ash specific surface area was
estimated to be 0.26 m2 g-1. The adsorption results showed that the COD removal was
up to 24% and the experimental result followed the Langmuir and Freundlich
isotherms.
The best isotherm, kinetic models and the maximum adsorption capacity was
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tabulated in Table 3.
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5. Thermodynamic studies
Most often, thermodynamic parameters such as Gibbs free energy (ΔG0) (Eqn.
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1), enthalpy change (ΔH0) (Eqn. 2) and entropy change (ΔS0) (Eqn. 3) are used in
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the solid/liquid interface. There are many ways to estimate the aforementioned
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parameters and in most cases, there is need to use necessary experimental data at three
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or more temperatures to estimate them. The ΔH0 and ΔS0 are obtained from the slope
and intercept of different plots like ln(bL) vs 1/T (in (L mol-1) from Langmuir model)
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to qe=0), or ln(K) vs 1/T (K=qmXbL calculated from Langmuir constant (qm), is the
maximum adsorption capacity in mg g-1 and bL units in L mg-1) and ln(qe/ce) vs 1/T
(qe/ce is the ratio where qe is adsorbed adsorbate at concentration (mg L-1) and ce is the
residual adsorbate concentration in the solution (mg L-1)). The reason to choose one
for the above methods is not explained (appeared) clearly in the works and with the
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and they also obtained a linearity when a plot of ΔS0 vs ΔH0 (Eqn. 3) is drawn where
G 0 RT ln K (1)
ΔG0 = ΔΗ 0 ΤΔS 0
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(2)
G 0 0
S
0
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(3)
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In Table 4, the thermodynamic parameters are tabulated for the adsorption of
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different aquatic pollutants by sugar industry wastes based adsorbents. As can be seen
(Table 4), sorption data, ranged from three to five temperatures (278–338 K) were
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used. Thermodynamic studies showed that in most cases, the adsorption was
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spontaneous or non-spontaneous (ΔG0 < 0, ΔG0 > 0, absolute value 0.32 to 33.31 kJ
mol-1), endothermic or exothermic (ΔH0 < 0, ΔH0 > 0, absolute values 0.091 to 66.3 kJ
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mol-1) with positive or negative entropy values (absolute value 0.001 to 0.22 kJ mol-1
K-1).
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Based on the Eq. 3 and on the thermodynamic data obtained from Table 4, a
plot of ΔHo versus ΔSo shows a strong linear relationship (R2>0.82) (Fig. 1) which is
ΔHo and ΔSo following adsorption due to the fact that the calculated thermodynamics
parameters the came from different studies with various experimental conditions [98].
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One possible explanation is that both ΔH0 and ΔS0 calculated from the same equation.
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6. Conclusions and future directions
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This paper presents the recent advances in the use of waste materials from
sugar industry as adsorbents and their performance in the removal of various aquatic
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pollutants. The study revealed that surface modification with chemicals greatly
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enhanced the removal efficiency of sugar wastes based adsorbents with favorable
kinetics and adsorption efficiency. The performance of the adsorbents largely depends
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on the type of pollutants and experimental conditions. Most of the studies aimed at
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estimating the maximum adsorption capacities using batch mode experiments using
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single synthetic pollutant solution. The adsorption process was found to be affected
time, solution pH, adsorbent dosage, temperature etc. Langmuir isotherm and pseudo-
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second kinetic model were found to show the best fit to the experimental data.
Columns studies and experiments with real wastewaters should be conducted in future
in order to evaluate the potential of sugar waste based adsorbents for real applications.
most applied isotherms and kinetic models, three parameters isotherm models and
diffusion kinetic models are highly recommended. There is also the need to further
utilize the SBP, SCB and their derivatives for the removal of other emerging
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dyes and heavy metals. Most studies paid no attention on the reusability of sugar
wastes based adsorbents. In order to make the adsorption process more economically
feasible, regeneration studies are also required. Based on the fact that adsorption
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application of sugar waste as adsorbents.
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Fig. 1: The enthalpy-entropy compensation plot for the works reviewed in the present
review article
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Table 1. The maximum monolayer adsorption capacity and the best-fitting isotherm and kinetic models for the adsorption of metals by sugar
wastes based adsorbents.
Maximum
Isotherm Kinetic
monolayer
P T
Adsorbents Metals
models models
R I
adsorption
capacity
Ref.
Sugarcane bagasse
Sugarcane bagasse
P T Cd2+
Cd2+
L Ps2 6.79 [29]
Sugarcane bagasse
C
Acrylic-modified sugarcane bagasse
E Cd2+
L
L
Ps2
Ps2
0.1865
304.878
[30]
[39]
A C
Activated carbons obtained from sugar beet pulp
Cd2+ L Ps2 68.03 [42]
impregnated with phosphoric acid (carbonized at 300 oC)
Activated carbons obtained from sugar beet pulp Cd2+ L Ps2 71.99 [42]
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P T
[31]
S C
Ps2 704.225 [39]
Pb2+
L
L
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Ps2
86.96
30.71
[44]
[46]
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Sugarcane bagasse colonized by Lentinula edodes (U6-1) Pb2+ L Ps2 42.67 [46]
Sugarcane bagasse
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colonized by Pleurotus ostreatus
A C
Sugarcane bagasse colonized by Ganoderma lucidum
Pb2+ L Ps2 43.27 [46]
(U12-6)
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Sugar beet pulp treated with NaOH and citric acid Cu2+ L Ps2 119.43 [35]
P T
Carbons obtained from sugar beet pulp (carbonized at 400
Cu2+ L Ps1
R I
13.44 [43]
o
C)
S C
Carbons obtained from sugar beet pulp (carbonized at 500
o
C)
Cu2+ L
NU Ps1 14.81 [43]
P T
Acrylic-modified sugarcane bagasse
C E Cu2+
Hg1+
L Ps2 265.252 [39]
A C
Pectin extracted from sugar beet pulp Hg2+
L, F
L
Ps2
-
35.71
19.8
[33]
[45]
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SCBPB-sugarcane bagasse pith beads Cr6+ L Ps2 832.13 [38]
a
b
Qm obtained from kinetic studies.
Qm obtained from batch studies.
P T
C
d
Qm obtained from Ps2 model.
Qm obtained from Ps1 model.
C E
A C
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based adsorbents.
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Table 2. The maximum monolayer adsorption capacity and best-fitting isotherm and kinetic models for the adsorption of dyes by sugar wastes
R I Maximum
SC
monolayer
Isotherm Kinetic
Adsorbents Dyes
N U
models models
adsorption
capacity
Ref.
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Reticulated formic lignin (RFL) from sugarcane bagasse (unbuffered,
pH=5.9)
P T MB L - 14.57 [67]
C E
Reticulated formic lignin (RFL) from sugar cane bagasse (buffered,
MB L - 15.72 [67]
pH=5.8)
A C
Reticulated formic lignin (RFL) from sugarcane bagasse (buffered,
MB L - 16.50 [67]
pH=4.5)
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Sugarcane bagasse MB L -
P T108.69 [52]
S C
Ps2 25.5a [61]
Sugarcane bagasse
Sugarcane bagasse
EB
MG
L,F
N
L
U -
Ps2
333.3
190
[51]
[55]
Sugarcane bagasse
M
MG A L Ps2 23.41 [57]
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Sugar cane bagasse MG F Ps2 5.71
[59]
Sugarcane bagasse
A C
Sugarcane bagasse pretreated with 0.1 mM CPBr
AO7
L,F
L,F
-
-
14.599
102.041
[60]
[60]
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P T
2.08 x 10-3 [65]
mol g-1
Quaternary ammonium modified-sugar beet pulp AR1 L Ps2
R I 1.92 x 10-4 [66]
mol g-1
Sugar beet pulp SA L
S C
Ps2 147b [53]
a
b
Adsorbed dye at equilibrium
Obtained from kinetic study N U
M A
E D
P T
C E
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Table 3. The maximum monolayer adsorption capacity and the best-fitting isotherm and kinetic models for the adsorption of miscellaneous
pollutants by sugar wastes based adsorbents.
Maximum
Isotherm Kinetic
P T
monolayer
Adsorbents Pollutants
models models
R I Adsorption
capacity
Ref.
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Phosphate L - 152 [75]
with Fe2+ ions
P T
Sugarcane bagasse
C
Activated carbon from sugarcane bagasse
E Fluoride
Phenol
F
L
Ps2
Ps2
2.168
47.92
[80]
[85]
A C
Chemically activated carbon from sugarcane bagasse Phenol L - 121.36 [85]
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a
Obtained from kinetic study
P T
R I
S C
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M A
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P T
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Τable 4. List of models for the adsorption isotherms and kinetics for adsorption of different pollutants on sugar waste based adsorbents.
P T
Raw sugar cane bagasse with 0.1 M oxalic acid Cu 2+
328
298
303
-19.83
-1.73
-2.32
I
26.42
R
0.094 [34]
308
313
S C
-2.68
-3.16
M
303
308
313
A -4.38
-5.07
-5.17
D
318 -5.53
2+
Dried sugar beet pulp Cu 298 -0.74 -66.3 -0.22 [32]
Sugarcane bagasse
T E EB 308
318
-0.38
-0.39
0.091 0.002 [51]
C C 313
323
-5.13
-4.26
Sugarcane bagasse
A MG 293
303
313
-3.86
-3.19
-2.52
-23.41 -0.067 [55]
323 -1.86
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308 13.35
318 14.30
Carbonaceous sugarcane baggase MG 303 -0.323 -6.92 0.001 [58]
308 -0.328
313 -0.332
C E 313.15
328.15
-24.31
-25.71
Carbonised beet pulp
A C Phenol 298
313
333
-21.57
-23.36
-25.04
6.35 0.095 [86]
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Graphical Abstract
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Highlights
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