Cationic and anionic dye adsorption by agricultural solid wastes: A comprehensive review by:

IOSR Journal of Applied Chemistry (IOSR-JAC)
e-ISSN: 2278-5736.Volume 5, Issue 3 (Sep. – Oct. 2013), PP 91-108
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Cationic and anionic dye adsorption by agricultural solid wastes:
A comprehensive review by:
Namit Tripathi
* Chemical Engg. Student ,Madhav Institute Of Technology And Science ,Gwalior 474005,Madhya
Pradesh ,India
Abstract: Dyes are an important class of pollutants, and can even be identified by the human eye. Disposal of
dyes in precious water resources must be avoided, however, and for that various treatment technologies are in
use. Among various methods adsorption occupies a prominent place in dye removal. Recently many researchers
have proved that agricultural solid wastes can be effectively used as adsorbents for the removal of many
pollutants including dyes. This review represents the effectiveness of agricultural solid wastes in the removal of
dyes, of cationic and anionic classes, description of classification of dyes and comparison among cationic and
anionic dyes adsorption by the same adsorbent, thus, possibly opening the door for a better understanding of the
dye classified adsorption process. Both these classes of dyes are toxic and cause severe problems to aquatic
environment. Some agricultural solid wastes can remove both dye classes. The dye adsorption capacities of
agricultural waste adsorbents vary along with the variation in pH of solution, initial dye concentration,
adsorbent dosage and process temperature. As the pH of the solution affects the surface charge of the adsorbent
and degree of ionization of the adsorbate, it is directly related to the dye classified adsorption. This review also
contains the table representing the adsorbent and subsequent dye/dyes appropriate for a particular process.
Conclusions have been drawn from the literature reviewed, and suggestions for future research are proposed.
I. Introduction:
Industrial developments in the recent years have left their impression on the environmental society.
Industries like textile industry uses dyes to color their products and thus produce waste water containing
organics where in the dyeing processes the percentage of the dye lost waste water is 50% of the dye because of
the low levels of dye fiber fixation [2]. Discharge of these dyes into effluents affects the people who may use
these effluents for living purposes such as washing, bathing and drinking [3]. Therefore it is very important to
verify the water quality, especially when eve just 1.0mg/L of dye concentration in drinking water could impart a
significant color, making it unfit for human consumption [4]. Dyes can affect the aquatic plants because they
reduce sunlight transmission through water. Dyes may impart toxicity to aquatic life and may be mutagenic,
carcinogenic and may cause severe damages to human beings, such as dysfunction of kidneys, liver, brain and
central nervous system [5-7].
There are more than 100,000 commercially available dye exist and more than 7x105 tones per year
are produced annually [8]. Wastewater containing dyes is very difficult to treat, since the dyes are recalcitrant
organic molecules, resistant to aerobic digestion, and are stable to light. A synthetic dye in wastewater cannot be
efficiently decolorized by traditional methods. This is because of the high cost and disposal problems for
treating dye wastewater at large scale in the textile and paper industries [9].
Removal of color from waste effluents is environmentally important because even a small quantity of
dye in water can be toxic and highly visible [10]. Since the removal of dyes from waste water is considered an
environmental challenge and government legislation requires textile waste water to be treated, therefore there is
a constant need of a process that can effectively remove these dyes [11].
In spite of the availability of many techniques to remove these pollutants from the waste water as legal
requirements, such as coagulation, chemical oxidation, membrane separation, electrochemical and aerobic and
anaerobic microbial degradation. These methods are not very successful due to many restrictions [12]. Among
all the different processes available, adsorption has been preferred due to its cheapness and the high quality of
the treated effluents, especially for well-designed sorption processes [13]. Adsorption by activated carbon is an
important way to clean up effluents and waste water [14], where, it used to polish the influent before it is
discharged into the environment [15].
However adsorption by activated carbon has some restrictions such as the cost of the activated carbon,
the need for regeneration after exhausting and the loss of adsorption efficiency after regeneration [16].
Therefore adsorption by agricultural by-products used recently as an economical and realistic method
for removal of different pollutants has proved to be an efficient at removing many types of pollutants such as
heavy metals [17,18], COD [19,120], phenol [21,22], gases [23] and dyes [24-27].

Cationic and anionic dye adsorption by agricultural solid wastes:A comprehensive review by:
In order to increase the adsorption capacity of the adsorbent, researchers have followed different
activation methods and they usually used the Langmuir isotherm to indicate the effectiveness of the activation
process. Activation methods involve physical activation such as carbonization of material and chemical
activation such as using chemical activating agents.
Real textile waste water is a mixture of dyes, organic compounds, heavy metals, total dissolved solids,
surfactants, salts, chlorinated compounds, COD and BOD [28,29].
Therefore some studies tested the agricultural wastes as adsorbents for these pollutants. Ahmad and
Hameed [20] studied the reduction of color and COD using bamboo activated carbon, and found that the
maximum reduction of color and COD were about 91.84% and 75.21%, respectively.
Anionic and cationic surfactants may effect on the dye adsorption depending on the dye type. The
adsorption of the basic dyes can be enhanced in the presence of anionic surfactant. On the other hand the
adsorption of anionic dyes can be enhanced in the presence of cationic surfactant. The negative ion of surfactant
may be adsorbed on the adsorbent by van der waal interaction and then the anionic dye can be adsorbed by the
anionic exchange. Although high concentrations of surfactants may cause aggregation or dye solubilization thus
decreases the dye adsorption [30,31].
Advantages and disadvantages of dye removal methods:
The table below shows the advantages and disadvantages of different techniques used for the removal of
dyes;
Technology Advantages Disadvantages
Conventional
treatment
processes
Coagulation
Flocculation
Simple, economically
feasible
High sludge production,
handling and disposal
problems
Biodegradation Economically attractive,
publicly acceptable
treatment
Slow process, necessary to
create an optimal favorable
environment, maintenance
and nutrition requirements
Adsorption on
activated carbons
The most effective
adsorbent, great,
capacity, produce a
high-quality treated
effluent
Ineffective against disperse
and vat dyes, the
regeneration is expensive
and results in loss of the
adsorbent, non-destructive
process
Established
recovery
processes
Membrane
separations
Removes all dye types,
produce a high-quality
treated effluent
High pressures, expensive,
incapable of treating large
volumes
Technology Advantages Disadvantages
Ion-exchange No loss of sorbent on
regeneration, effective
Economic constraints, not
effective for disperse dyes
Oxidation Rapid and efficient
process
High energy cost, chemicals
required
Emerging
removal
processes
Advanced
oxidation
process
No sludge production,
little or no consumption
of chemicals, efficiency
for recalcitrant dyes
Economically unfeasible,
formation of by-products,
technical constraints
Selective
bioadsorbents
Economically attractive,
regeneration is not
necessary, high
selectivity
Requires chemical
modification, nondestructive
process
Biomass Low operating cost,
good efficiency and
selectivity, no toxic
effect on
microorganisms
Slow process, performance
depends on some external
factors (pH, salts)

Classification and characteristics of dyes:
This table below shows types of dyes and their description;
Dye
Class
Description Method
Fibers
Typically
Applied to
Typical
Fixation
(%)
Typical Pollutants
Associated with Various
Dyes
Acid water-soluble anionic compounds Exhaust/ Beck/
Continuous (carpet)
wool, nylon 80-93 color; organic acids; unfixed
dyes
Basic water-soluble, applied in weakly
acidic dyebaths; very bright dyes
Exhaust/ Beck acrylic, some
polyesters
97-98 N/A
Direct water-soluble, anionic
compounds;can be applied directly
to cellulosics without mordants (or
metals like chromium and copper)
Exhaust/
Beck/Continuous
cotton, rayon,
other
cellulosics
70-95 color; salt; unfixed dye;
cationic fixing agents;
surfactant; defoamer; leveling
and retarding agents; finish;
diluents
Disperse not water-soluble High temperature
exhaust Continuous
polyester,
acetate, other
synthetics
80-92 color; organic acids; carriers;
leveling agents; phosphates;
defoamers; lubricants;
dispersants; delustrants;
diluents
Reactive water-soluble, anionic compounds;
largest dye class
Exhaust/ Beck Cold
pad batch/
Continuous
cotton, other
cellulosics,
wool
60-90 color; salt; alkali; unfixed dye;
surfactants; defoamer;
diluents; finish
Sulfur organic compounds containing
sulfur or sodium sulfide
Continuous cotton, other
cellulosics
60-70 color; alkali; oxidizing agent;
reducing agent; unfixed dye
Vat oldest dyes; more chemically
complex; water-insoluble
Exhaust/Package/
Continous
cotton, other
cellulosics
80-95 color; alkali; oxidizing agents;
reducing agents
Cationic dyes:
Cationic dyes are widely used in acrylic, wool, nylon and silk dyeing [32]. These dyes include different
chemical structures based on substituted atomic groups [33]. These types of dyes are considered as toxic
colorants and can cause harmful effects such as allergic dermatitis, skin irritation, mutations and cancer [34].
These dyes are also called basic dyes and depend on the positively charged ion, which are generally
hydrochloride or zinc chloride complexes [35]. Cationic dyes carry a positive charge in their molecule [36],
furthermore it is water soluble and yield colored cations in solution. Basic dyes are highly visible and have high
brilliance and intensity of colors [37]. Cationic functionality is found in cationic azo dyes and methane dyes,
also in anthraquinon, di- and tri-arylcarbenium, phthalocyanine dyes, various polycarbocyclic and solvent dyes
[38]. Cationic dyes were used intensely as a model in dye adsorption studies such as crystal violet [39],
methylene blue [40,41], basic blue 41 [42] and basic red 46 [43]. methylene blue is an important basic dye and
widely used in the textile industry. Acute exposure to methylene blue may cause increased heart rate, shock,
vomiting, cyanosis, jaundice, quadriplegia, Heinz body formation and tissue necrosis in humans [44]. Many
researchers have studied the adsorption of methylene blue dye using agricultural wastes such as peanut hull [45],
castor seed shell [46], coconut shell [47], guava leaf [48], neem leaf [49] and gulmohar plant [50], where the dye
adsorption capacities were 123.5, 158, 277.9, 295, 351, 186.22 mg/g respectively. All these wastesshowed
goodadsorption capacities for methylene blue dye adsorption.
Anionic dyes:
Anionic dyes depend on the negatively charged ions [35]. Anionic dyes include many compounds from
the most varied dye classes having characteristic differences in structure (e.g., azoic, anthraquinone,
triphenylmethane and nitro dyes) but posses as a common feature, water-solubilizing, ionic substituents. The
anionic dyes also include direct dyes, and from the chemical standpoint the group of anionic azo dyes includes a
large proportion of reactive dyes [38]. Most of the reactive dyes interact with cotton, wool, etc., to form covalent
forms. The release of the reactive dyes into the environment is undesirable, because they have a low degree of
fixation due to the hydrolysis of reactive groups in the water phase [51]. Acid dyes are hydrophilic and used
with silk, wool, polyamide, modified acrylic and polypropylene fibres. Acid dyes are harmful for humans since
they are organic sulphonic acids [52].

Dye removal adsorbents:
Many adsorbents have been used for the removal of the dyes from the waste water. Adsorption of dyes
depends on the properties of the dye and the surface chemistry of the adsorbent [53].
The adsorption process is one of the effective methods for removal dyes from the waste effluent. The
process of adsorption has an edge over the other methods due to its sludge free clean operation and completely
removed dyes, even from the diluted solution. Activated carbon (powdered or granular) is the most widely used
adsorbents because it has excellent adsorption efficiency for the organic compound. Nevertheless, commercially
available activated carbon is very expensive. Furthermore, regeneration using solution produced small
additional effluent while regeneration by refractory technique results in a 10-15% loss of adsorbents and its
uptake capacity [54]. The sorption data have been correlated with adsorption isotherm to determine the
efficiency of adsorption process. Numerous researchers worked earlier on variety of adsorpents as mentioned
below. Wool Fiber and Cotton Fiber [55], Banana pith [56,57], Biogas residual slurry [56], Carbonized coir pith
[58], Coir pith [59], Chitosan [60], Hardwood [61], Mahogany sawdust, rice husk [62], Parthenium
hysterophorus [63], Neem (Azadirachta Indica) husk [64], Rice husk [65], Rice husk [66],
Silk cotton hull, coconut tree sawdust [67], Gypsum [68], Tuberose Sticks [69], Tamarind Fruit Shell[70],
Some of the adsorbents are peanut hull, sugar beet pulp, rice husk ash, coir pith, tea waste, almond shells,
lemon peel, bagasse fly ash, neem sawdust, guava seed carbon, etc., .The most widely used adsorbent for the
dye removal is activated carbon. Coal, charcoal and sawdust can be the raw material for the production of the
commercial activated carbon where the activation includes partial oxidation and pore structure develops. Two
types of activated carbon can be produced which are H-type and L-type. H-type is positive charge upon water
and hydrophobic while L-type assumes a negative charge in water and hydrophilic [71-73].
Activated carbon can be available in granular form (granular activated carbon (GAC)). GAC can be
prepared from hard materials that used to remove water pollutants because its adaptability for continuous
contacting and because there is no need to separate the intraparticular diffusion in GAC is a problem
encountered in the application of adsorption processes to water treatment.
Activated carbon can also be available in powdered form (powdered activated carbon (PAC)). PAC can
be obtained when small particles compose the raw materials and normally mixed with the liquid to be treated
and then disposed off; therefore the use of PAC requires the separating of carbon from fluid after use. Yet the
PAC used for waste water treatment because of low cost and less contact time, where it presents a large external
surface and a small diffusion distance [74,75].
Agricultural Solid Wastes:
There have been many attempts to find inexpensive and easily available adsorbents to remove the
pollutants such as agricultural solid wastes where according to their physic-chemical characteristics and low
cost they may be good potential adsorbents [76].
Agricultural productions are available in large quantities around the world; thus big amount of waste
rejected [77]. Agricultural wastes are lignocellulosic materials that consist of three main structural components
which are lignin, cellulose and hemicelluloses. These components contribute mass and have high molecular
weights. Lignocellulosic materials also contain extractive structural components which have a smaller molecular
size [78].
Different adsorbents derived from agricultural solid wastes have been used for dye removal from waste
water and many studies of dye adsorption by agricultural solid wastes have been published. Some of the
agricultural solid wastes like sugarcane bagasse [79], sugarcane bagasse ash [80], rice husk [81], fly ash [82],
activated carbon from coir pith [83], pineapple stem waste [84], orange peel [85], mesoporous carbon [86],
hardwood sawdust [87], clay, wall nut shell [88], coconut husk [89], coal fly ash [90], cow dung [91], wheat
dust [91], activated carbon prepared from mosambi peel [92]etc. are used as adsorbents for the removal of dyes
from the waste water.
Agricultural wastes are renewable, available in large amounts and less expensive as compared to other
materials used as adsorbents. Agricultural wastes are better than other adsorbents because the agricultural wastes
are usually used without or with a minimum of processing (washing, drying, grinding) and thus reduce
production costs by using a cheap raw material and eliminating energy costs associated with thermal treatment
[93].
Oil palm has been recently utilized in many industrial fields, therefore a large amount of waste is
generated from these industries and many studies make use of these by-products as dye adsorbents, such as palm
kernel fiber [94, 95], palm shell [96] and palm kernel shell [97].
Coconut is grown in more than 80 countries of the world and its products are applied in food industries,
and as a result many wastes are generated from these industries and used intensely for dye adsorption studies
such as empty coconut bunch [98], coconut-husk [99], coconut coir dust [100] and coconut tree sawdust [101].

On the other hand, there are abundant agricultural wastes which have a good adsorption capacity for dye
adsorption but are little used as adsorbents such as pomelo peel (Citrus grandis) [102], castor seed shell [103],
shells of bittim (Pistacia khinjuk stocks) [104] and jatropha husk [105].
Adsorbent Dyes References
Sugar beet pulp German turquoise blue-G [106]
Powdered peanut hull Sunset yellow, Amaranth and Fast
green
[107]
Rice husk ash Indigo Carmine [108]
Chemically modified peanut hull
Methylene blue, Brilliant cresyl blue,
Neutral red, sunset yellow and fast
green.
[109]
Peanut hull
Methylene blue, brilliant cresyl blue,
neutral red.
[110]
Coir pith activated carbon
Reactive orange 12, reactive red 2,
reactive blue 4 and Congo red.
[111,112]
Coir pith carbon Methylene blue [113]
ZnCl2 activated coir pith carbon
Acid brilliant blue, Acid violet,
methylene blue and Rhodamine B.
[114]
Coir pith Acid violet [115]
Rice husk activated carbon Malachite green
[116]
Rice husk based porous carbon Malachite green
[117]
Rice husk Congo red
[118]
Tea waste Methylene blue
[119]
Coniferous pinus bark powder Crystal violet
[120]
Orange peel activated carbon Direct N Blue-106
[121]
Neem Sawdust Malachite green
[122]
Guava seed carbon Acid Blue 80
[123]
Peanut hull Reactive Black 5
[124]
Loofa activated carbon Reactive orange
[125]
Apricot stone activated carbon Astrazon Yellow (7GL)
[126]
Almond shells Direct red 80
[127]
Lemon peel Malachite green
[128]
Bagasse fly ash Methyl violet
[129]
Polygonum orientale Linn activated
carbon
Malachite green
[130]
Effect of adsorption factors on dye uptake:
II. Effect of solution pH:
pH is a measure of acidity or basicity of an aqueous solution. The pH factor is very important in the
adsorption process especially for dye adsorption. The pH of a medium will control the magnitude of electrostatic
charges which are imparted by the ionized dye molecules. As a result the rate of adsorption will vary with the
pH of an aqueous medium [131]. The effect of pH solution on the adsorption process can be studied by prepare
adsorbent–adsorbate solution with fixed adsorbent dose and dye concentration but with different pH by adding
NaOH (1 M) or HCl (1 M) solutions and then shaken until equilibrium. Generally, at low pH solution, the

percentage of dye removal will decrease for cationic dye adsorption, while for anionic dyes the percentage of
dye removal will increase. In contrast, at a high pH solution the percentage of dye removal will increase for
cationic dye adsorption and decrease for anionic dye adsorption.
At high pH solution, the positive charge at the solution interface decreases and the adsorbent surface
appears negatively charged [132]. As a result, the cationic dye adsorption increases and anionic dye adsorption
shows a decrease. In contrast, at a low pH solution, the positive charge on the solution interface will increase
and the adsorbent surface appears positive charged, which results in an increase in anionic dye adsorption and a
decrease in cationic dye adsorption. Osma et al. [133] studied the effect of solution pH on the adsorption of
Reactive black 5 dye by sunflower seed shells and they noticed that at a pH range from 2 to 4, the dye removal
ratio was minimal at a pH 4. Aksu and Isoglu [106] studied the effect of solution pH on the adsorption of
Gemazol turquoise blue-G as a reactive dye using sugar beet pulp and they noticed that the adsorption was at
maximum at pH 2 where the adsorption capacity was 83.7 mg/g and then decreased with a further increase in
pH and reached zero at pH 6. Hameed et al. [134] studied the adsorption of Methylene blue (MB) dye as a
cationic dye by banana stalk and they noticed that the adsorption of MB was at minimum at pH 2 and maximum
at pH 4.
The results shown in several descriptions, except for the removal of Rhodamine-B dye using orange
peel waste, where the percentage of dye removal decrease with increasing pH value. Rhodamine B dye (RhB)
(C28H31N2O3Cl) is basic, red colored and has two molecular forms (Cationic and Zwitterionic form) [135]. Its
chemical structure is shown in Fig. 1 Rhodamine B dye is used in textile and food industries, where it has a high
solubility in water and it is a water tracer for biological stains and fluorescents. A few publications have the
same result of the pH effect on Rhodamine-B dye adsorption, where Gad et al. [136] studied the adsorption of
Rhodamine B dye by bagasse pith activated carbon and they concluded that at a high pH the zwitterionic form
of RhB is responsible for the aggregation increase, where according to Guo et al. [137], the increase of
aggregation of Rhodamine-B dye may form a bigger molecular form and become unable to enter into the
adsorbent pore.
Effect of pH and different dosage of orange peel under alkaline conditions are depicted in Figures given below;
Figure 1: Effect of pH under alkaline conditions at regular time interval [85].
Figure 2: Effect of pH under alkaline conditions at various adsorbent dosages [85].

Figure 3: Chemical structure of Rhodamine B dye: (a) Cationic form and (b) Zwitterionic Form.
The isoelectric point (pI) or point of zero charge is an important factor that determines the linear range of pH
sensitivity and then indicates the type of surface active centers and the adsorption ability of the surface [138].
Many researchers studied the isoelectric point (pI) of adsorbents that prepared from agricultural solid
wastes in order to better understand of adsorption mechanism. Cationic dye adsorption is favored at pH>pI, due
to presence of functional groups such as OH−, COO− groups. Anionic dye adsorption is favored at pH<pI where
the surface becomes positively charged [139,140].
In order to determine the pI, dye solutions with different range of pH should prepare and consider as
pHinitial then fix amount of adsorbent should be added to the solutions.
These solutions should be shaken until equilibrium where the pH at equilibrium considers pHfinal, then
plot the pH(final) values against pH(initial) where pI is the point when pH(initial) = pH(final) [141].
Karagöz et al. [142] studied the adsorption of Methylene blue (MB) onto sunflower oil cake activated
carbon and they found that the zero point of charge (pI) for the activated carbon lies between pH 2.5 and 5.5,
while the maximum adsorption capacity of Methylene Blue (MB) was at pH 6, in other word pH>pI.
Vieira et al. [143] studied the adsorption of Blue Remazol (R160) onto babassu coconut mesocarp and
they found that the zero point of charge (pI) for the babassu coconut mesocarp was 6.7, while the maximum
adsorption capacity of Blue Remazol R160 was at pH 1, in other word pH<pI
Figure 4: Effect of solution pH on the adsorption of Methylene blue on banana stalk waste.

III. Effect of initial dye concentration:
The effect of initial dye concentration can be carried out by prepare adsorbent–adsorbate solution with
fixed adsorbent dose and different initial dye concentration for different time intervals and shaken until
equilibrium.
The percentage removal of dye is highly dependent on the initial amount of dye concentration. The
effect of the initial of dye concentration factor depends on the immediate relation between the concentration of
the dye and the available binding sites on an adsorbent surface. Generally the percentage of dye removal
decreases with an increase in the initial dye concentration, which may be due to the saturation of adsorption sites
on the adsorbent surface [144]. At a low concentration there will be unoccupied active sites on the adsorbent
surface, and when the initial dye concentration increases, the active sites required for adsorption of the dye
molecules will lack [46]. On the other hand the increase in initial dye concentration will cause an increase in the
loading capacity of the adsorbent and this may be due to the high driving force for mass transfer at a high initial
dye concentration [145]. Garg et al. [146] studied the adsorption of Methylene blue by sulphuric acid treated
sawdust (SDC) at an adsorbent dose of (0.4 g/100 mL), at a temperature of (26±1 °C) and at pH (7.0) and they
found that the unit adsorption for SDC increased from 12.49 mg/g to 51.4 mg/g as the Methylene blue
concentration was increased from 50 mg/L to 250 mg/L, while the percentage of dye removal decreased from
99.9% to 82.2% as the Methylene blue concentration was increased from 50 mg/L to 250 mg/L. Table 6 shows
previous studies on the effects of initial dye concentration on the percentage of dye removal according to the
dye class, and it is obvious that the percentage removal of both dyes (cationic and anionic) decreases with
increasing initial dye concentration.
Real textile wastewaters includes high concentration of dyes, which highest than the concentrations
that used in literatures, therefore researchers used empirical design procedures based on adsorption equilibrium
conditions in order to predict the adsorber size and performance [Fig. 5].
Figure 5: Single stage batch adsorber design
The design objective is to reduce the dye solution of volume V (L) from an initial concentration of Cï to C1
(mg/L). The amount of adsorbent is M (g) and the solute loading changes from qï to q1 (mg/g). At time t=0,
qï=0 and as time proceeds the mass balance equates the dye removed from the liquid to that picked up by the
solid. The mass balance equation for the sorption system in can be written as:
V (Cο−C1) = M(qo – q1) = Mq1
Vadivelan and Kumar [147] studied the adsorption design of Methylene blue removal using rice husk and they
found that the amount of rice husk required removing 90% of Methylene blue solution of concentration 100
mg/L was 3.828, 7.655, 11.482 and15.309g for dye solution volumes of 1, 2, 3 and 4 L, respectively.
Adsorption process design model has been developed for the design of two-stage batch adsorber [Fig.
4] and can save adsorbent to meet the needs for higher dye removal efficiency and minimize capital investment
costs [148]. Özacar et al. [149] studied the adsorption design of Metal complex yellow dye removal using pine
sawdust and they found that single stage process needs more time from two-stage process, where the required
time for 75–90% dye removal in single stage increased 4–15 min.

Figure 6: Multi-stage batch adsorption process for dye removal.
IV. Effect of adsorbent dosage:
The effect of adsorbent dosage on the adsorption process can be carried out by prepare adsorbent–
adsorbate solution with different amount of adsorbents added to fixed initial dye concentration then shaken
together until equilibrium time.
Usually the percentage of dye removal increases with increasing adsorbent dosage, where the number of
sorption sites at the adsorbent surface will increase by increasing the dose of the adsorbent [150], and as a result
increase the percentage of dye removal from the solution. Study of the effect of adsorbent dosage gives an idea
of the effectiveness of an adsorbent and the ability of a dye to be adsorbed with a minimum dosage, so as to
identify the ability of a dye from an economical point of view. Sonawane and Shrivastava [151] studied the
effect of adsorbent dose on the removal of Malachite green by maize cob and they concluded that at 20 mg/L of
dye, pH of 8 and a contact time of 25 min, the increase of percentage of dye removal from 90.0% to 98.5%
when the adsorbent dose increased from 0.5 to 12 g/L. Table 7 shows previous studies of the effect of adsorbent
dosage on the percentage of dye removal according to the dye class, and it is obvious that the percentage of both
dyes (cationic and anionic) increase with increasing the adsorbent dosage. Some experimental data for orange
peel, neem leaves, banana peel and activated carbon is shown below in graph;
Figure 7: Comparative results of various Adsorbents on to Effect of Adsorbent Dosage.
Effect of temperature:
The effect of temperature on the adsorption process can be carried out by prepare adsorbent–adsorbate
solution with different initial dye concentration then shaken together until equilibrium time at 30, 40 and 50 °C.
Temperature is an indicator for the adsorption nature whether it is an exothermic or endothermic process. If
the adsorption capacity increases with increasing temperature then the adsorption is an endothermic process.
This may be due to increasing the mobility of the dye molecules and an increase in the number of active sites for
the adsorption with increasing temperature [152]. This effect depends mainly on the movement of dye
molecules of each dye class. The decrease of adsorption capacity with increasing temperature indicates that the
adsorption is an exothermic process [153]. Increasing temperature may decrease the adsorptive forces between
the dye species and the active sites on the adsorbent surface as a result of decreasing adsorption capacity [94].
Senthilkumaar et al. [112] studied the adsorption of Crystal violet (CV) on phosphoric and sulphuric
acid activated carbons (PAAC and SAAC), prepared from male flowers coconut tree. They conclude that the
adsorption capacities increased with temperature increasing [Fig. 5]. Önal [154] studied the adsorption of
Methylene blue (MB), Malachite green (MG) and Crystal violet (CV) by carbon prepared from waste apricot
and he concluded that the adsorption rate of the three dyes may be enhanced by increasing the adsorption
temperature. Hameed and Ahmad [155] studied the adsorption of Methylene blue (MB) by garlic peel and they

found that the adsorption capacity increased from 82.64 to 142.86 mg/g when the temperature increased from
30 °C to 50 °C indicating that the adsorption is endothermic. Previous studies on the effect of temperature on the
nature of the adsorption process according to the dye class shows that the adsorption of anionic and cationic
dyes by each adsorbent increases with increasing temperature, indicating the adsorption is an endothermic
process, except for the adsorption of (4Bromoanilineazo-1,8-di-hydronaphthalene-3,6-di-sodiumsulphate(BDH))
by palm kernel fiber, since the adsorption of cationic dye is endothermic, while the adsorption of anionic dye is
exothermic, where according to Ofomaja and Ho the decrease in the adsorption capacity with increasing
temperature is due to the weakening of the sorptive forces between the active sites on the sorbent and the dye
species, and also between adjacent dye molecules on the adsorbed phase.
Figure 8: Effect of temperature on the removal of Crystal violet on PAAC and SAAC
V. Effect of time:
As a result of many experiments performed by different scientists is being observed that the dye
removal efficiency on an adsorbent varies with the time. Variation may be of both nature either positive or
negative that means dye removing efficiency of an adsorbent may increase or decrease with course of time.
Some graphical data from the experiment performed on orange peel, neem leaves, banana peel, activated carbon
and papita saha(tamarind fruit shell,2010) is given below;
Figure 9: Comparative results of various adsorbents on to Effect of time.[85]
Adsorption isotherm:
The adsorption isotherm is important for the description of how the adsorbate will interact with the
adsorbent and give an idea of the adsorption capacity of the adsorbent. The surface phase may be considered as
a monolayer or multilayer. Langmuirian kinetic is based on the ideal monolayer adsorbed model [156]. The

Langmuir isotherm is the most popular isotherm model and it is used to describe the adsorption process where
the occupancy occurs at on one adsorption site at an energetically homogeneous range of adsorption sites [157].
The expression of the Langmuir isotherm equation is represented
by the following equation
q(e) = q(max.)K(l)C(e)/1+K(l)C(e)
q(e)— Amount of adsorbate adsorbed at equilibrium (mg/g)
q(max) - Maximum monolayer adsorption capacity of the adsorbent
(mg/g)
C(e) — Equilibrium concentration of adsorbate (mg/L)
K(l)— Langmuir adsorption constant related to the free energy
adsorption (L/mg)
Studies of the Langmuir isotherm for anionic and cationic dye adsorption by various agricultural
adsorbents generally shows, the adsorption capacity for cationic dye adsorption is higher than anionic dye
adsorption on the same adsorbent except for the pinewood. Since the carboxyl group is one of the major
functional groups in agricultural wastes, it will have an effect on the adsorption capacity according to the dye
class. The carboxyl group bears a negative charge, and therefore it is the major functional group in the
adsorption of cationic dyes. On other hand it will inhibit the adsorption of anionic dyes [158]. Namane et al.
[159] studied the adsorption of Acid blue dye as an anionic dye and Basic yellow dye as a cationic dye by coffee
grounds, and they concluded that the basic yellow dye is adsorbed faster and has a better uptake than the acid
blue dye.
Kumar et al. [160] studied the adsorption of Bismark brown dye by activated carbons prepared from
rubber wood sawdust using different activation methods. They studied the chemical activation carbon
(impregnated with phosphoric acid and activated in a fixed bed at 400 °C for 1 h), steam-activation (activated in
a fluidized bed reactor at 750 °C for 1 h with a steam flow rate of 4 mL min−1) and chemical activation
followed by steam carbon (the char was impregnated with phosphoric acid (0.45) IR and activated in a fluidized
bed at 800 °C for 1 h with a steam flow rate of 5 mL min−1). The concluded that the steam-activated carbon was
a better choice to remove the dye as it had higher adsorption capacity (2000 mg/g).
Tseng [161], studied the removal of Acid blue 74 (AB74), Basic brown 1(BB1), Methylene blue (MB)
and Phenol by activated carbon prepared from plum kernels. The activation of plum kernels char was done by
NaOH activation at six different NaOH/char ratios. NaOH/char ratio is defined as PKN0, PKN0.5, PKN1,
PKN2, PKN3, and PKN4, where trailing numeric value represents the weight of NaOH/char ratio. The surface
area obtained per unit activation agent (SP/agent ratio) of PKN2 was the highest. Although the adsorption
capacity of PKN4 was the highest to remove all the four adsorbates but the value of KLCi, was suggested by the
researcher to evaluate a favorable level, where Ci is the highest initial adsorbate concentration (mg/L). Tseng
[113]121 found that the values of KLCi for the adsorption of MB, AB74, BB1 and phenol by PKN2 were
392,65, 49 and 20 respectively. He concluded that the KLCi value of adsorption of MB is in the hundreds and
therefore extremely favorable; adsorption of AB74, BB1, and phenol are in the tens, and therefore is highly
favorable; while if KLCi value is a single digit, then it is favorable and if it is a decimal then it is weakly
favorable.
Wu et al. [162] studied the adsorption of AB74, BB1, MB and 4-Chloropenol (4-CP) by fir wood
activated carbon by NaOH (soaked in a concentrated NaOH solution, oven-dried and activated with different
NaOH/char weight ratio (2, 3 and 4)). They concluded that the maximum adsorption capacity values for the
adsorption of AB74 and BB1 by FWNa4 were the highest and those for the adsorption of MB and 4-CP by
FWNa3 were the highest.
Altenor et al. [163] studied the adsorption of Methylene blue and Phenol by vetiver roots activated
physically (carbonization) and chemically (different impregnation ratios of phosphoric acid (gH3PO4/g
precursor): (0.5:1); (1:1) and (1.5:1)). They used four isothermmodels to study the adsorption isotherm:
Freundlich, Langmuir, Redlich– Peterson and Brouers–Sotolongo equations. The data was a best fit with the
Brouers–Sotolongo equation and with the Redlich–Peterson equation. They concluded that the chemically
activated samples had a higher adsorption capacity than the physically activated samples for the removal of MB
dye and the adsorption capacities of the adsorbent with an activation ratio of (1.5:1)) were 423 mg/g and 444
mg/g for the Langmuir and Brouers–Sotolongo models.

Adsorption kinetics:
The dynamics of the adsorption can be studied by the kinetics of adsorption in terms of the order of the
rate constant [164]. The adsorption rate is an important factor for a better choice of material to be used as an
adsorbent; where the adsorbent should have a large adsorption capacity and a fast adsorption rate. Most of
adsorption studies used Pseudo-first-order and Pseudo-second-order models to study the adsorption kinetics. For
the Pseudo-first-order model, the adsorption rate was expected to be proportional to the first power of
concentration, where the adsorption was characterized by diffusion through a boundary. The Pseudo-first-order
model sometimes does not fit well for the whole range of contact time when it failed theoretically to predict the
amount of dye adsorbed and thus deviated from the theory. In that case, the Pseudo-second-order equation used
was based on the sorption capacity of the solid phase, where the Pseudo-second-order model assumes that
chemisorption may be the rate-controlling step in the adsorption processes [165,166].
For the Pseudo-first-order model (Lagergren model) under initial and end boundary conditions t=0to t=t and
qt=0to qt=qt, a linear equation is obtained:
Log[q(e) – q(t)] = log[q(e)] – K(1).t/2.303
For the Pseudo-second-order model under the initial and end boundary conditions t=0 to t = t and qt = 0 to qt
= qt, a linear equation is obtained:
t/q(t) = 1/K(2).q(e).q(e) + t/q(e)
q(t) — The amount of adsorbate adsorbed at time t (mg/g)
q(e) — The amount of adsorbate adsorbed at equilibrium (mg/g)
k(1) — The pseudo-first-order rate constant of adsorption (1/h) or
(1/min)
K(2) — The pseudo-second-order rate constant of adsorption
(g/mg h) or (g/mg min)
Usually the best-fit model can be selected based on the linear regression correlation coefficient R2
values. Generally the kinetic adsorption is better represented by Pseudo-second-order model for anionic and
cationic dye adsorption. Lakshmi et al. [167] evaluated the adsorption of Indigo carmine dye by rice husk ash.
They found that the values of the Pseudo-first-order rate constant increases from 0.0087 to 0.0122 min-1 with an
increasing initial dye concentration from 50 to 500 mg/L, which indicates that the adsorption rate increases with
an increase in initial dye concentration while the R2 values were closer to unity for the Pseudo-second-order
model than that for the Pseudo-first-order model. Bulut and Aydin [145] investigated the adsorption of
Methylene blue using wheat shells and they found that the values of the constants for the Pseudo-first and
Pseudo-second order models were increased with increasing temperature and the R2 values for second order
model were greater than 0.999 indicating the second-order nature of the adsorption process. Ponnusami et al.
[48] studied the use of guava leaf powder for adsorption of Methylene blue. They found that the values of R2 of
the Pseudo-first-order model were between 0.70 and 0.85, while the values of R2 for the second order model
were 0.999, indicating the conformity of second order model. Pavan et al. [168] studied the adsorption of
Methylene blue by yellow passion fruit waste and they found that the Pseudo-first-order model was better fitted
than the Pseudo-second-order kinetic, where the lower standard deviation of the residues for the Pseudo-first-
order model were (b0.49 mg g-1) and the R2 value was 0.9906. Table 9 shows previous kinetic studies of
cationic and anionic dyes adsorption by various agricultural adsorbents and it shows that the kinetic studies
followed the Pseudo-second-order model.
Desorption study:
In order to regenerate the adsorbent and recovery the adsorbed compounds, desorption process
necessary to be study were also desorption study help to explain the adsorptionmechanism.Desorption rate is
proportional to the driving force and desorption kinetics is very important for the contaminant transport
modeling [169-171].
Desorption process usually done by mixing a suitable solvent with the dye-saturated substrate and
shaken together for fixed time, until the dye extract on the solvent and then using filtration to separate the
adsorbent. The dye–solvent mixture dried at high temperature to evaporate the solvent. The desorbed dye then
determine in spectrophotometer [172].
Robinson et al. [172] studied the desorption of Cibarcon red from corncob using mixture of methanol,
chloroform and water. They found that the maximum value of desorption was 93%.

María et al. [173] studied the desorption of three classes of textile dyes from maize waste and they found
that the adsorption efficiencywas minor for reactive dyes at the same time the desorption was
higher in comparison with the basic dye. They found that the reactive blue 235 can be recovered up to 40% by
using warm water as solvent.
Won et al. [174] studied the desorption of Reactive black 5 from Corynebacterium,
Glutamicum waste biomass and they found that the desorption efficiency was lower at almost 80% compared to
100% of adsorption efficiency.
Kumar and Ahmad [175] studied the desorption of Crystal violet dye from ginger waste and they found
that NaOH and H2O did not showed any desorption while acetic acid desorbed about 35–50% of dye.
Mahmoodi et al. [176] studied the desorption of three textile dyes from pinecone and they concluded that
the maximum desorption for Acid black 26, Acid green 25 and Acid blue 7 was 93.16%, 26.97% and 98%,
respectively.
VI. Conclusion:
The literature reviewed revealed the fact that there has been a high increase in production and
utilization of dyes in last few decades resulting in a big threat of pollution. It is worthwhile noting that the
removal of dyes can be done by various techniques; however, there exists no such methodology which can
successfully remove all types of dyes at low cost. The literature survey results and the methods discussed above
lead us to the conclusion that for removal of dyes adsorption can give fruitful results. During the last few years
many articles concerning the adsorption of dyes by agricultural solid wastes have been published, therefore a lot
of assumptions and results exist. This paper is an attempt to highlight the effect of the dye class on the
adsorption process and review some of the studies of dye adsorption on agricultural wastes according to the dye
class. This review makes a simple comparison between the cationic and anionic dye removal using agricultural
byproducts. It can be concluded that the agricultural wastes are effective adsorbents for cationic and anionic
dyes, but in their natural form, the agricultural wastes are better for adsorbing the cationic dyes rather than the
anionic dyes. In most cases these adsorbents require a treatment process to enhance their capability for anionic
dye removal.
The most important factor that affects dye-classified adsorption is the pH factor,where a high pHvalue
is preferred for cationic dye adsorption while a low pH value is preferred for anionic dye adsorption. Previous
studies showed that cationic dye adsorption was favored at pHNpHpzc, while, anionic dye adsorption was
favored at pHbpHpzc. It was also noticed that the effect of adsorbent dose with respect to the concentration of
dye is effective for cationic and anionic dye removal. The Langmuirmodel is usually used to evaluate the
adsorption capacity of the agricultural wastes as adsorbents and most of studies of dye adsorption by agricultural
solid wastes showed a higher adsorption capacity for cationic dyes than an adsorption capacity for anionic dyes.
The kinetic data of adsorption of cationic and anionic dyes onto agricultural solid wastes usually follows the
Pseudo-second-order model. Cost comparison between the cationic and anionic dye adsorptionby agricultural
solidwastes is animportant need in order to evaluate the dye-classified adsorption process from the economic
point of view.
The literature review shows that there is a need for more detailed systematic studies on dye removal
process and also some technical improvements in preparing and utilizing adsorbent. As regards to future work,
the following recommendations are suggested.
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