PROJECT REPORT

on
Kinetics of adsorptive Removal of CBSOL Red LE Dye on to Activated Carbon
Submitted in partial fulfillment of the requirement for the award of
degree of
Bachelor of Engineering
in
Chemical Engineering

SUBMITTED BY

Ashwini kumar prince

(ROLL No.-101181001)
Under the guidance
of
Dr. J. P. Kushwaha
(Assistant Professor)
Department of Chemical Engineering
Thapar University, Patiala

Department of chemical engineering

Thapar University, Patiala
Patiala (Punjab)-147004
January, 2014

CERTIFICATE
This is to certify that the project report entitled Kinetics of adsorptive Removal of CBSOL
Red LE Dye on to Activated Carbon, is an authentic record of my own work carried out as
requirements for the award of degree of B.E. in Chemical Engineering from Thapar University,
Patiala, under the supervision of Dr. J. P. Kushwaha, Assistant Professor, Department of
Chemical Engineering, Thapar University, Patiala, during July 2013 to January 2014.

Date: _____________

Ashwini Kumar Prince

(Roll No: 101181001)

It is certified that the above statement made by the student is correct to the best of our
knowledge and belief.

Dr. J.P. Kushwaha

Assistant Professor
Department of Chemical Engineering
Thapar University, Patiala

Countersigned by:
Dr. Rajeev Mehta
Associate professor and
HeadDepartment of Chemical Engineering
Thapar University, Patiala, Punjab

ABSTRACT
Adsorption of CBSOL Red LE dye on granular activated carbon (GAC) from
aqueous solutions was studied. The potential for the adsorption of CBSOL RED LE dye at a
fixed initial concentration of 100 ppm and 50 ppm on GAC was carried out, and kinetic
study was conducted at optimized set of operational parameters like pH, time and adsorbent
dose. The kinetics of adsorption of CBSOL RED LE dye from aqueous solution onto
activated carbon has been investigated. The time dependent studies showed a rapid
adsorption in the initial time. A batch sorption model based on the assumption of the pseudo
first and second order mechanism, were applied to predict the rate constants. The adsorption
process follows the pseudo-second order kinetic, having a correlation coefficient 0.99. The
pseudo second order rate constant ks was found to generally increase from 0.012 to 0.018 as
the initial concentration increased from 50 to 100 ppm. In case of pseudo-first order kinetic
the value of kf also increases from 0.021 to 0.035 as the initial concentration increased from
50 to 100 ppm.

ACKNOWLEDGEMENT

I would like to make my deepest appreciation and gratitude to Dr. J. P. Kushwaha for
his valuable guidance, constructive criticism and encouragement during every stage of this
project.
I am accreted to offer my thanks to the department of chemical engineering, Thapar
University, Patiala for allowing my training under the sincere guidance of tentative faculty
members
I am

grateful

to Dr. Rajeev Mehta , Head

Engineering for providing me

of

the Department, Chemical

the necessary opportunities for

the completion of my

project. I also thank other staff members of my department for their invaluable help and
guidance.

(Ashwini kumar Prince)

 CONTENTS
S. No.

Particulars

1 INTRODUCTION

Page Number
1

1.1 Industrial impacts on water

1.2 Characteristics and applications of reactive dye

1
1

1.3 Methods of removal of reactive dye

1.4 Activated carbon

1.5 Adsorption versus other methods

1.6 Objective

11

2 LITERATURE VEIW

12

3 MATERIALS AND METHODS

30

3.1 Waste water

30

3.2 Analytical methods

30

3.3 Experimental programme

31

3.4 Kinetics of adsorption

31

4 RESULTS AND DISCUSSIONS

4.1 Adsorption experiment

33
33

5 CONCLUSION

36

6 REFERENCES

37

INTRODUCTION

1.1 General
Rrapid development has improved the standard of living and quality of life for millions of
peoples the world over. This development has come at the cost of a thirty-fold increase in the
use of fossil fuels and a fifty-fold increase in industrial production over the 2 past centuries.
As a result, significant amounts of existing natural resources have been consumed by
industry, leaving the earth depleted for future generations. The requirement of fresh water for
industrial use will increase from 30 BCM (Billion Cubic Meters) to 120 BCM by 2025 AD
[1]. Much of the waste produced from these activities is directly discharged into natural
water bodies. One of the major challenges facing mankind today is to provide clean water
around the world.
1.2 Characteristics and application of reactive dye
1.2.1 Properties of Reactive Dye:
1. Reactive dyes are cationic dyes, which are used for dyeing cellulose, protein and
polyamide fibres.
2. Reactive dyes are found in power, liquid and print paste form.
3. During dyeing the reactive group of this dye forms covalent bond with fibre polymer and
becomes an integral parts of the fibre.
4. Reactive dyes are soluble in water.
5. They have very good light fastness with rating about 6. The dyes have very stable
electron arrangement and can protect the degrading effect of ultra-violet ray.
6. Textile materials dyed with reactive dyes have very good wash fastness with rating about
4-5 due to strong covalent bonds formed between fibre polymer and reactive group of
dye.
7. Reactive dye gives brighter shades and has moderate rubbing fastness.
8. Dyeing method of reactive dyes is easy. It requires less time and low temperature for
dyeing.
9. Reactive dyes are comparatively cheap.
10. Reactive dyes have good perspiration fastness with rating 4-5. Reactive dyes have good
perspiration fastness [2].
1

1.2.2 Composition of reactive dye

Various chemicals are used in dyeing with reactive type dyes. These chemicals and their uses are
as follows.

Dye Fixer: Dye fixer is a chemical called sodium carbonate. The fixer is the one
chemical you absolutely must have to make these dyes work. Fixer causes the important
chemical reaction that makes these dyes become part of the fabric. In direct application
dyeing such as tie dyeing, the fabric is first soaked in a solution of dye fixer dissolved in
water. In vat dyeing, solid color dyeing, the dye fixer is added to the dye bath near the
end of the dyeing process. In tie dyeing, we estimate that one pound of dye fixer will
make approximately 20 adult T-shirts. A 5 pound bag will make approximately 100 Tshirts. In solid color dyeing, one pound fixer will color about 6 pounds of dry fabric.

Urea: Urea is used in tie dyeing or other direct application dyeing. It is generally not
used in Vat (solid color) dyeing. Urea does many things to help the dyeing process. Urea
helps large amounts of dye dissolve in small amounts of water. Urea helps the dye
penetrate the fabric. Moisture is an important component of the chemical reaction process
with these dyes, and urea helps draw moisture to the chemical reaction. We estimate that
on pound of urea will tie dye about 16 to 18 T-shirts. 5 pounds of urea will therefore tie
dye about 80 shirts.

Ludigol: Ludigol is used in tie dyeing or other direct application dyeing. It is generally
not used in Vat dyeing. Once reactive dye is mixed with water, it slowly starts to break
down in the water. When this happens, over time the dye becomes less effective. Soon
the dye solution will lose all effectiveness. Ludigol is added to the dye to keep the dye
from reacting with, or breaking down in the water. It keeps the dye fresher longer, and
allows more dye to react with the fabric. Helping the colors to come out brighter. We
estimate that 2 ounces of ludigol with tie dye about 60 T-shirts. Therefore, an 8 ounce
bag should dye around 240 T-shirts.

Water Softener: Dyes work better in soft water. Water softener is used in both tie dye
and solid color dyeing. One 8 ounce bag of water softener will tie dye approximately 160
shirts.

Sodium alginate: Sodium alginate is used to thicken dye mixtures for hand painting and
silk screening. Most of our customers do not use sodium alginate unless they have a
specific reason that they want thicker dye mixtures. Two ounces of our sodium alginate
will thicken about 8 quarts of water to a hand painting consistency.

Synthrapol detergent: Synthrapol detergent is used to wash out loose dye after the
fabric is dyed. Synthrapol is used to wash out different colored dyes, as in tie dyes and
keep those dyes from staining other parts of the fabric. Using Synthrapol is the best way
to ensure that your colors will stay pure during wash out, and that your white areas will
remain relatively white. One 16 ounce bottle of synthrapol will wash 8 to 24 wash loads
[3].

1.2.3

General structure of reactive dye

The general structure of reactive dye is: D-B-G-X.
Here,

D= dye part or chromogen (color producing part)

Dyes may be direct, acid, disperse, premetallised dye etc.
B = bridging part.
Bridging part may be NH- group or NR- group.
G = reactive group bearing part.
X= reactive group.

Figure 1.1: Chemical structure of reactive dye [2]

1.2.4

USES OF DYE

Rective dyes are used extensively in food, clothing, paints, plastics, etc.

dye in food
One other class that describes the role of dyes, rather than their mode of use, is the food
dye. Because food dyes are classed as food additives, they are manufactured to a higher
standard than some industrial dyes. Food dyes can be direct, mordant and vat dyes, and
their use is strictly controlled by legislation. Many are azo dyes, although anthraquinone
and triphenylmethane compounds are used for colors such as green and blue. Some
naturally-occurring dyes are also used.

dye in painting of clothes

Use PRO H-Reactive Dyes for Traditional Silk Painting with a resist. This technique can
also be used on Cotton, Linen and Rayon. We've found that H-Liquid Dye has an
improved flow property over powdered H Dyes, producing even fluid color.

dye in plastics
reactive dye is used in dying of buckets ,bottels,households etc [4].
4

1.3 Methods for removal of reactive dye

The methodologies generally adopted to treat dye wastewater in four categories:
(i)

physical

(ii)

chemical

(iii)

biological

(iv)

accoustical, radiation, and electrical processes. Some of the methodologies lying in

above mentioned categories are discussed in brief in subsequent paragraphs.

Sedimentation is the basic form of primary treatment used at most municipal and
industrial-wastewater treatment facilities (Cheremisinoff, 2002). There are a number of
process options available to enhance gravity settling of suspended particles, including
chemical flocculants, sedimentation basins, and clarifiers.

Filtration technology is an integral component of drinking water and wastewater

treatment applications which includes microfiltration, ultrafiltration, nanofiltration, and
reverse osmosis. This has been investigated for colour removal

Chemical treatment of dye wastewater with a coagulating/flocculating agent (Shi et al.,

2007, Wang et al., 2006a and Zhou et al., 2008) is one of the robust ways to remove
colour. The process involves adding agents, such as aluminum (Al3+), calcium (Ca2+) or
ferric (Fe3+) ions, to the dye effluent and induces flocculation.

Oxidation is a method by which wastewater is treated by using oxidizing agents.

Generally, two forms viz. chemical oxidation and UV assisted oxidation using chlorine,
hydrogen peroxide, fenton's reagent, ozone, or potassium permanganate are used for
treating the effluents, especially those obtained from primary treatment (sedimentation).
They are among the most commonly used methods for decolourisation processes since
they require low quantities and short reaction times. They are used to partially or
completely degrade the dyes

Electrochemical methodology (Gupta et al., 2007b and Lin and Peng, 1994) as a tertiary
treatment is also used to remove colour. Decolorisation can be achieved either by electro
oxidation with non-soluble anodes or by electro-coagulation using consumable materials.
Several anode materials, like iron, conducting polymer a boron doped diamond electrode
etc., with different experimental conditions, have been used successfully in the electrodegradation of dyes
5

Biological treatment is the most common and widespread technique used in dye
wastewater treatment (Barragan et al., 2007, Bromley-Challenor et al., 2000, dos Santos
et al., 2007, Frijters et al., 2006, van der Zee and Villaverde, 2005 and Zhang et al.,
1998). A large number of species have been used for decolouration and mineralization of
various dyes. The methodology offers considerable advantages like being relatively
inexpensive, having low running costs and the end products of complete mineralization
not being toxic. The process can be aerobic (in presence of oxygen), anaerobic (without
oxygen) or combined aerobicanaerobic [5].

1.4 Activated carbon

Activated carbon, is the oldest adsorbent known and is usually prepared from coal,
coconut shells, lignite, wood etc., using one ofthe two basic activation methods: physical and
chemical (Bansal et al., 1988 [6]; Carrott et al., 2003 [7]; Hassler, 1963 [8]; Lillo-Rodenas et
al.,2007 [9]; Phan et al., 2006 [10]). Generally, the physical activation requireshigh temperature
and longer activation time as compared tochemical activation, however, in chemical activation
the AC needa thorough washing due to the use of chemical agents. A schematicdiagram of the
process of producing activated carbons generallyadopted by workers is shown in Figure 1.2.
The product formed by either of the methods is known as activated carbon and normally
has a very porous structure with a large surface area ranging from 500 to 2000 m2 g_1 (Carrott et
al., 1991 [11]). It has been found that adsorption on activated carbon is not usually selective as it
occurs through van der Waals forces.
The ability of charcoal to remove odour and taste was recorded centuries ago. The
literature (Freeman, 1989; Tien, 1994 [12]) shows that according to a Sanskrit manuscript from
circa 200 BC, It is good to keep water in copper vessels, to expose it in sunlight and to filter it
through charcoal. However, the credit of developing commercial activated carbon (Smsek
and Cern_y, 1970 [13]) goes to Raphael von Ostrejko whose inventions were patented in 1900
and 1901.

Figure 1.2: Schematic diagram of the process of producing activated carbons generally
adopted by workers

Source.
The applicability of activated carbon for water treatment has been demonstrated by
various workers (Stenzel, 1997 [14]; Weber Jr. et al., 1970 [15]). Besides these, various authors
(Bansal and Goyal, 2005 [16]; Hassler, 1963 [17]) have discussed and summarized in their book
the successful applications of activated carbons. Activated carbon is available in two main forms:
powdered activated carbon (PAC) and granular activated carbon (GAC). Most of the work on the
7

removal of pollutants from water has been on GAC, due to the fact that the granular form is more
adaptable to continuous contacting and there is no need to separate the carbon from the bulk
fluid.
On the other hand, the use of PAC presents some practical problems because of the
requirement to separate the adsorbent from the fluid after use. However, in spite of these
problems PAC is also used for wastewater treatment due to low capital cost and lesser contact
time requirement (Najm et al., 1991 [18]). Besides PAC and GAC two other forms of ACs are
also available, Activated Carbon Pellet and Activated Carbon Fiber (ACF). The pelletized
activated carbons are generally prepared from coal where coal is pulverized and reagglomerated
with suitable binder and then physically activated.These materials are made especially for use in
vapor applications. They are normally available in sizes of 1.5, 3 and 4 mm diameter. For ACF,
the carbon fibers are generally prepared from polymeric precursor materials such as
polyacrylonitrile(PAN), cellulose, pitch and polyvinylchloride; of these PAN based carbon fibers
pre-dominate and have good strength and modulus properties, whereas carbon fiber can be made
with a higher modulus, albeit a lower strength, using a pitch-based precursor.
These carbon fibers after activation using same methodology results in high surface area
carbons. The activated carbons which are used as adsorbents, not onlyremove different types of
dyes (Al-Degs et al., 2001[19]; DiGiano and Natter,1977 [20]; Pelekani and Snoeyink, 2000
[21]; Walker andWeatherley,1999 [22]), but also other organic and inorganic pollutants such as
metal ions (Carrott et al.,1998,1997 [23],[24]; Gabaldon et al., 2000 [25]; Kuennen et al.,1992
[26]; Macias-Garcia et al., 1993 [27]), phenols (Carrott et al., 2005 [28]; Caturla et al., 1988
[29]; Mourao et al., 2006 [30]; Paprowicz et al., 1990 [31]; Zogorski et al., 1976 [32]),
pesticides (Hu et al., 1998 [33]; Pirbazari et al., 1991 [34]; Pirbazari and Weber Jr., 1984 [35]),
chlorinated hydrocarbons (Urano et al., 1991 [36]), humic substances (Lee et al., 1983 [37]),
PCBs (Pirbazari et al., 1992 [38]), detergents (Bele et al., 1998 [39]; Malhas et al., 2002 [40]),
organic compounds which cause taste and odour (Flentje and Hager 1964 [41]; Lalezary et al.,
1986 [42]) and many other chemicals and organisms (Annesini et al., 1987 [43]; Carrott et al.,
2000 [44]; Donati et al., 1994 [45]; Giusti et al., 1974 [46]; McKay et al., 1985a [47]; Najm et
al., 1993 [48]; Saito, 1984 [49]; Smith,1991 [50]). It is well known that adsorption by activated
carbon is an effective and commercially applicable method for removing colour and other
pollutants from textile and dye wastes.
8

Studies have shown that activated carbons are good materials for the removal of different
types of dyes in general but there use is sometimes restricted in view of higher cost. Also, the
activated carbons after their use (treatment of wastewater) become exhausted and are no longer
capable of further adsorbing the dyes. Once AC has been exhausted, it has to be regenerated for
further use in purifying water and a number of methods like thermal, chemical, oxidation,
electrochemical (Freeman, 1989 [51]; Hemphill et al., 1977 [52]; Kilduff and King, 1997 [53];
Martin and Ng, 1987 [54]; Narbaitz and Cen, 1994 [55]; Newcombe and Drikas, 1993 [56];
Notthakum et al., 1993 [57]; Rollar et al., 1982 [58]; Taiwo and Adesina, 2005 [59]; Zhou and
Lei, 2005 [60]) are used for this purpose, the most common being thermal. It is worthwhile
noting that regeneration of activated carbon adds cost, furthermore, any regeneration process
results in a loss of carbon and the regenerated product may have a slightly lower adsorption
capacity in comparison with the virgin activated carbon.

1.5 Adsorption Vs other methods

Among various water purification and recycling technologies, adsorption is a fast,
inexpensive and universal method. The development of low-cost adsorbents has led to the rapid
growth of research interests in this field. The present protocol describes salient features of
adsorption and details experimental methodologies for the development and characterization of
low-cost adsorbents, water treatment and recycling using adsorption technology including batch
processes and column operations. The protocol describes the development of inexpensive
adsorbents from waste materials, which takes only 12 days, and an adsorption process taking
15120 min for the removal of pollutants. The applications of batch and column processes are
discussed, along with suggestions to make this technology more popular and applicable.

Table 1.1: Adsorption capacity of various adsorbents.

Adsorbent

Adsorption capacity (mg/g)

AC-Charcoal

101

AC Rice husk

50

Modified silica

45.8

Peat

12.7

Treated cotton

589

Bagasse pith(raw)

17.5

Wood

7-11.6

Pine sawdust (raw)

280.3

Activated sewage sludge

60.04

Activated clay

57.8

Banana pith

4.42

Coir pith (raw)

16.67

Activated bentonite

360.5

Coal

0.7691

Fly ash

0.7428

Rice husk carbon

86.9

Sawdust carbon

183.8

Pine sawdust (raw)

398.8

Orange peel (raw)

19.88

Lignite coal (raw)

30.9

Orange peel

20.5

Source: V.K. Gupta et al., 2009 [61]

10

1.6 Objective
To study the adsorption kinetics of CBSOL Red LE dye on Activated carbon from the
aqueous solution in batch study.

11

2 LITERATURE REVIEW
In this chapter, various adsorption studies of reactive dye on activated carbon have
been reviewed.
Vinod K. Gupta et al., (2007) studied the removal of Vertigo Blue 49 and Orange
DNA13 from aqueous solutions using carbon slurry developed from a waste material. Waste
material (carbon slurry), from fuel oil-based generators, was used as adsorbent for the removal of
two reactive dyes from synthetic textile wastewater. The study describes the results of batch
experiments on removal of Vertigo Blue 49 and Orange DNA13 from synthetic textile
wastewater onto activated carbon slurry. The utility of waste material in adsorbing reactive dyes
from aqueous solutions has been studied as a function of contact time, temperature, pH, and
initial dye concentrations by batch experiments. pH 7.0 was found suitable for maximum
removal of Vertigo Blue 49 and Orange DNA13. Dye adsorption capacities of carbon slurry for
the Vertigo Blue 49 and the Orange DNA13 were 11.57 and 4.54 mg g1 adsorbent,
respectively. The adsorption isotherms for both dyes were better described by the Langmuir
isotherm. Thermodynamic treatment of adsorption data showed an exothermic nature of
adsorption with both dyes. The dye uptake process was found to follow second-order kinetics
[62].
S. Nethaji et al., (2011) studied adsorptive removal of an acid dye by lignocellulosic
waste biomass activated carbon. Chemically prepared activated carbon material derived from
palm flower was used as adsorbent for removal of Amido Black dye in aqueous solution. Batch
adsorption studies were performed for the removal of Amido Black 10B (AB10B), a di-azo acid
dye from aqueous solutions by varying the parameters like initial solution pH, adsorbent dosage,
initial dye concentration and temperature with three different particle sizes such as 100 m,
600 m and 1000 m. The zero point charge was pH 2.5 and the maximum adsorption occurred
at the pH 2.3. Experimental data were analyzed by model equations such as Langmuir,
Freundlich and Temkin isotherms and it was found that the Freundlich isotherm model best fitted
the adsorption data and the Freundlich constants varied from (KF) 1.214, 1.077 and 0.884 for the
three mesh sizes. Thermodynamic parameters such as G, H and S were also calculated for
the adsorption processes and found that the adsorption process is feasible and it was the
endothermic reaction. Adsorption kinetics was determined using pseudo first-order, pseudo
12

second-order rate equations and also Elovich model and intraparticle diffusion models. The
results clearly showed that the adsorption of AB10B onto lignocellulosic waste biomass from
palm flower (LCBPF) followed pseudo second-order model, and the pseudo second-order rate
constants varied from 0.059 to 0.006 (g mg1 min) by varying initial adsorbate concentration
from 25 mg L1to 100 mg L1. Analysis of the adsorption data confirmed that the adsorption
process not only followed intraparticle diffusion but also by the film diffusion mechanism [63].
Liang-Gui Wang et al ., (2011) investigated the adsorptive removal of direct yellow
161dye from aqueous solution using bamboo charcoals activated with different chemicals. The
adsorption of direct yellow 161 dye from aqueous solution on derived bamboo charcoals
activated with orthophosphoric acid, nitric acid, potassium hydroxide and zinc chloride was
investigated. Batch adsorption results showed that under optimal sorption condition including
initial dye concentration 24.62 mg/L, pH 1.0, contact time 21 h, and temperature 298 k the
maximum and the minimum adsorption capacities were 2.401 mg/g and 1.705 mg/g for bamboo
charcoals activated with orthophosphoric acid and with potassium hydroxide, respectively.
Avrami kinetic model provided the best fit to experimental data compared with Elovich, pseudofirst-order, pseudo-second-order and intra-particle diffusion models. Fitting of the equilibrium
data using Langmuir, Freundlich, Jovanovic, Khan and Koble-Corrigan isotherm models
indicated that Koble-Corrigan model was the best and three-parameter models gave better fitting
than two-parameter models did. Thermodynamic parameters revealed that the adsorption process
was spontaneous and endothermic with a physical nature. Compared with the other activated
bamboo charcoals the bamboo charcoal activated with orthophosphoric acid was the best
adsorbent for removal of direct yellow 161 dye [64].
Attouti Salima et al.,(2013) studied application of Ulva lactuca and Systoceira
stricta algae-based activated carbons to hazardous cationic dyes removal from industrial
effluents. Marine algae Ulva lactuca (ULV-AC) and Systoceira stricta (SYS-AC) based
activated carbons were investigated as potential adsorbents for the removal of hazardous cationic
dyes. Both algae were surface oxidised by phosphoric acid for 2 and subsequently air activated at
600 C for 3 h. Dyes adsorption parameters such as solution pH, contact time, carbon dosage,
temperature and ionic strength were measured in batch experiments. Adsorption capacities of
400 and 526 mg/g for Malachite green and Safranine O by the SYS-AC and ULV-AC
respectively were significantly enhanced by the chemical treatments. Model equations such as
13

Langmuir, Freundlich and Temkin isotherms were used to analyse the adsorption equilibrium
data and the best fits to the experimental data were provided by the first two isotherm models.
BET, FT-IR, iodine number and methylene blue index determination were also performed to
characterize the adsorbents. To describe the adsorption mechanism, kinetic models such as
pseudo-second-order and the intra particle diffusion were applied. Thermodynamic analysis of
the adsorption processes of both dyes confirms their spontaneity and endothermicity. Increasing
solution ionic strength increased significantly the adsorption of Safranine O. This study shows
that surface modified algae can be an alternative to the commercially available adsorbents for
dyes removal from liquid effluents [65].
S. Senthilkumaar et al., (2006) studied the adsorption of dissolved Reactive red dye
from aqueous phase onto activated carbon prepared from agricultural waste. The adsorption of
Reactive red dye (RR) onto Coconut tree flower carbon (CFC) and Jute fibre carbon (JFC) from
aqueous solution was investigated. Adsorption studies were carried out at different initial dye
concentrations, initial solution pH and adsorbent doses. The kinetic studies were also conducted;
the adsorption of Reactive red onto CFC and JFC followed pseudosecond-order rate equation.
The effective diffusion coefficient was evaluated to establish the film diffusion mechanism.
Quantitative removal of Reactive red dye was achieved at strongly acidic conditions for both the
carbons studied. The adsorption isotherm data were fitted well to Langmuir isotherm and the
adsorption capacity were found to be 181.9 and 200 mg/g for CFC and JFC, respectively. The
overall rate of dye adsorption appeared to be controlled by chemisorption, in this case in
accordance with poor desorption studies [66].
Yahya S. Al-Degs et al., (2008) studied the effect of solution pH, ionic strength, and
temperature on adsorption behavior of reactive dyes on activated carbon. The adsorption
behavior of C.I. Reactive Blue 2, C.I. Reactive Red 4, and C.I. Reactive Yellow 2 from aqueous
solution onto activated carbon was investigated under various experimental conditions. The
adsorption capacity of activated carbon for reactive dyes was found to be relatively high. At pH
7.0 and 298 K, the maximum adsorption capacity for C.I. Reactive Blue 2, C.I. Reactive Yellow
2 and C.I. Reactive Red 4 dyes was found to be 0.27, 0.24, and 0.11 mmol/g, respectively. The
shape of the adsorption isotherms indicated an L2-type isotherm according to the Giles and
Smith classification. The experimental adsorption data showed good correlation with the
Langmuir and Ferundlich isotherm models. Further analysis indicated that the formation of a
14

complete monolayer was not achieved, with the fraction of surface coverage found to be 0.45,
0.42, and 0.22 for C.I. Reactive Blue 2, C.I. Reactive Yellow 2 and C.I. Reactive Red 4 dyes,
respectively. Experimental data indicated that the adsorption capacity of activated carbon for the
dyes was higher in acidic rather than in basic solutions, and further indicated that the removal of
dye increased with increase in the ionic strength of solution, this was attributed to aggregation of
reactive dyes in solution. Thermodynamic studies indicated that the adsorption of reactive dyes
onto activated carbon was an endothermic process. The adsorption enthalpy (Hads) for C.I.
Reactive Blue 2 and C.I. Reactive Yellow 2 dyes were calculated at 42.2 and 36.2 kJ/mol,
respectively. The negative values of free energy (Gads) determined for these systems indicated
that adsorption of reactive dyes was spontaneous at the temperatures under investigation (298
328 K) [67].
Fernando M. Machado et al., (2011) studied the adsorption of Reactive Red M-2BE
dye from water solutions by multi-walled carbon nanotubes and activated carbon. Multi-walled
carbon nanotubes and powdered activated carbon were used as adsorbents for the successful
removal of Reactive Red M-2BE textile dye from aqueous solutions. The adsorbents were
characterised by infrared spectroscopy, N2 adsorption/desorption isotherms and scanning
electron microscopy. The effects of pH, shaking time and temperature on adsorption capacity
were studied. In the acidic pH region (pH 2.0), the adsorption of the dye was favourable using
both adsorbents. The contact time to obtain equilibrium at 298 K was fixed at 1 h for both
adsorbents. The activation energy of the adsorption process was evaluated from 298 to 323 K for
both adsorbents. The Avrami fractional-order kinetic model provided the best fit to the
experimental data compared with pseudo-first-order or pseudo-second-order kinetic adsorption
models. For Reactive Red M-2BE dye, the equilibrium data were best fitted to the Liu isotherm
model. Simulated dye house effluents were used to check the applicability of the proposed
adsorbents for effluent treatment [68].
Gehan M. Nabil et al., (2013) studied the enhanced decolorization of reactive black 5
dye by active carbon sorbent-immobilized-cationic surfactant (AC-CS). Activated carbonimmobilized-cationic surfactant (AC-CS) was designed to enhance the decolorization behavior
of reactive black 5 (RB5), as an anionic dye, from aqueous and industrial wastewater samples in
presence of various controlling experimental conditions. Experimental data indicated that the dye
adsorption capacity by (AC-CS) was higher in strongly acidic and basic solutions. An anion
15

exchange and ionion interaction mechanisms were proposed in the acidic solution, while only
anion exchange mechanism was suggested in the basic aqueous solution. The adsorption
behavior and thermodynamic parameters were also evaluated. Treatments of textile industrial
wastewater and real water samples were successfully established (95.23100.00%) [69].
Nevine Kamal Amin et al., (2008) studied the removal of reactive dye from aqueous
solutions by adsorption onto activated carbons prepared from sugarcane bagasse pith. Bagasse
pith, which is the main waste from sugarcane industry in Egypt, has been used as a raw material
for the preparation of different activated carbons. Activated carbons were prepared from bagasse
pith by chemical activation with 28% H3PO4 (AC1), 50% ZnCl2 (AC2) followed by pyrolysis at
600C and by physical activation at 600C in absence of air (AC3). Different activated carbons
have been used for the removal of reactive orange (RO) dye from aqueous solutions. Batch
adsorption experiments were performed as a function of initial dye concentration, contact time,
adsorbent dose and pH. Adsorption data were modeled using the Langmuir and Freundlich
adsorption isotherms. Adsorption kinetic data were tested using pseudo-first-order, pseudosecond-order and intraparticle diffusion models. Kinetic studies showed that the adsorption
followed pseudo-second-order reaction with regard to the intraparticle diffusion rate [70].
K.Santhy et al., (2006) studied the removal of reactive dyes from wastewater by
adsorption on coir pith activated carbon. The removal efficiency of activated carbon prepared
from coir pith towards three highly used reactive dyes in textile industry was investigated. Batch
experiments showed that the adsorption of dyes increased with an increase in contact time and
carbon dose. Maximum decolorisation of all the dyes was observed at acidic pH. Adsorption of
dyes was found to follow the Freundlich model. Kinetic studies indicated that the adsorption
followed first order and the values of the Lagergren rate constants of the dyes were in the range
of 1.77 1022.69 102 min1. The column experiments using granular form of the carbon
(obtained by agglomeration with polyvinyl acetate) showed that adsorption efficiency increased
with an increase in bed depth and decrease of flow rate. The bed depth service time (BDST)
analysis carried out for the dyes indicated a linear relationship between bed depth and service
time. The exhausted carbon could be completely regenerated and put to repeated use by elution
with 1.0 M NaOH. The coir pith activated carbon was not only effective in removal of colour but
also significantly reduced COD levels of the textile wastewater [71].

16

Palanivel Sathishkumar et al ., (2012)

studied the utilization of agro-industrial

waste Jatropha curcas pods as an activated carbon for the adsorption of reactive dye Remazol
Brilliant Blue R (RBBR) . Jatropha curcas is a non-edible oil crop predominately used to
produce biodiesel. J. curcas pod contains 80% as dried vegetable and remaining 20% are seeds
that are used for the biodiesel production in industries. In the present study, J. curcas pods were
used for activated carbon preparation and successfully employed as adsorbent for the removal of
reactive dye, Remazol Brilliant Blue R (RBBR). Batch adsorption experiments were performed
as a function of contact time, pH, adsorbent dosage and initial dye concentration. The
experimental results indicate that 0.2 g of activated carbon removed 95% of 50 mg L1dye.
Adsorption data were modeled using the Langmuir and Freundlich isotherms. Langmuir isotherm
was obeyed for the adsorption. Equilibrium parameter value (RL) was observed to be in the
range of 01. The dye adsorption followed the pseudo-first-order kinetics model with regard to
the intraparticle diffusion rate. Physico-chemical properties of activated carbon were analyzed by
SEM, FTIR and XRD before and after dye adsorption. The adsorbed dye from activated carbon
was successfully desorbed (80%) by 1 N NaOH. Bench scale removal of RBBR dye as well as
real textile effluent was carried out by J. curcas pods activated carbon (JCPAC). This option will
make the agro-industrial waste JCPAC adopted in textile industrial effluent treatment for
environmental cleansing [72].
A.A. Ahmad et al., (2010) studied the fixed-bed adsorption of reactive azo dye onto
granular activated carbon prepared from waste. In this work, the adsorption potential of bamboo
waste based granular activated carbon (BGAC) to remove C.I. Reactive Black (RB5) from
aqueous solution was investigated using fixed-bed adsorption column. The effects of inlet RB5
concentration (50200 mg/L), feed flow rate (1030 mL/min) and activated carbon bed height
(4080 mm) on the breakthrough characteristics of the adsorption system were determined. The
highest bed capacity of 39.02 mg/g was obtained using 100 mg/L inlet dye concentration, 80 mm
bed height and 10 mL/min flow rate. The adsorption data were fitted to three well-established
fixed-bed adsorption models namely, Adam'sBohart, Thomas and YoonNelson models. The
results fitted well to the Thomas and YoonNelson models with coefficients of
correlation R2 0.93 at different conditions. The BGAC was shown to be suitable adsorbent for
adsorption of RB5 using fixed-bed adsorption column [73].

17

Natali

F.

Cardoso et

al.,

(2012)

studied

the

comparison

of Spirulina

platensis microalgae and commercial activated carbon as adsorbents for the removal of Reactive
Red 120 dye from aqueous effluents. Spirulina platensis microalgae (SP) and commercial
activated carbon (AC) were compared as adsorbents to remove Reactive Red 120 (RR-120)
textile dye from aqueous effluents. The batch adsorption system was evaluated in relation to the
initial pH, contact time, initial dye concentration and temperature. An alternative kinetic model
(general order kinetic model) was compared with the traditional pseudo-first order and pseudosecond order kinetic models. The equilibrium data were fitted to the Langmuir, Freundlich and
Liu isotherm models, and the thermodynamic parameters were also estimated. Finally, the
adsorbents were employed to treat a simulated dye-house effluent. The general order kinetic
model was more appropriate to explain RR-120 adsorption by SP and AC. The equilibrium data
were best fitted to the Liu isotherm model. The maximum adsorption capacities of RR-120 dye
were found at pH 2 and 298 K, and the values were 482.2 and 267.2 mg g1 for the SP and AC
adsorbents, respectively. The thermodynamic study showed that the adsorption was exothermic,
spontaneous and favourable. The SP and AC adsorbents presented good performance for the
treatment of simulated industrial textile effluents, removing 94.499.0% and 93.697.7%,
respectively, of the dye mixtures containing high saline concentrations [74].
Ali Rza Diner et al., (2007) studied the comparison of activated carbon and bottom
ash for removal of reactive dye from aqueous solution. The adsorption of reactive dye from
synthetic aqueous solution onto granular activated carbon (GAC) and coal-based bottom ash
(CBBA) were studied under the same experimental conditions. As an alternative to GAC, CBBA
was used as adsorbent for dye removal from aqueous solution. The amount of Vertigo Navy
Marine (VNM) adsorbed onto CBBA was lower compared with GAC at equilibrium and dye
adsorption capacity increased from 0.71 to 3.82 mg g1, and 0.73 to 6.35 mg g1 with the initial
concentration of dye from 25 to 300 mg l1, respectively. The initial dye uptake of CBBA was
not so rapid as in the case of GAC and the dye uptake was slow and gradually attained
equilibrium [75].
Jae-Wook Lee et al., (2006) studied the evaluation of the performance of adsorption
and coagulation processes for the maximum removal of reactive dyes. Physicochemical
processes of adsorption and coagulation were systematically evaluated for the removal of
reactive dyes (Orange 16 and Black 5) in a laboratory scale experimental setup. The
18

effectiveness of combined processes of adsorption and coagulation for complete removal of dyes
was also investigated. The right sequence of operation was identified for the combined treatment
system. A coconut-based powdered activated carbon (PAC) was used as an adsorbent and alum
chloride was chosen as a coagulant. The results indicated that adsorption capacity of Orange 16
was much higher than that of Black 5. Also, adsorption capacity on PAC was highly dependent
on the pH of solution. The dye removal efficiencies for 100 mg l1 of Black 5 and Orange 16 by
coagulation were almost 99% and 80% under the determined optimal conditions for Black 5
(250 mg l1 coagulant dose and pH 6) and for Orange 16 (350 mg l1 coagulant dose and pH 6).
Coagulation followed by adsorption was found to be more efficient than having adsorption prior
to coagulation. There was a significant increase in adsorption capacity of PAC for the combined
process where coagulation was carried out prior to adsorption. The combined coagulation
adsorption process has the capability of complete dye removal and thus total decolourization,
reduction in coagulant and adsorption amounts and thereby produce less amount of sludge [76].
Wen-Hong Li et al., (2011)., studied the preparation and utilization of sludge-based
activated carbon for the adsorption of dyes from aqueous solutions. Sludge-based activated
carbon (SAC) was prepared from paper mill sewage sludge by carbonization at low temperature
followed by physical activation with steam in this study and the utilization of SAC in removing
Methylene Blue (MB) and Reactive Red 24 (RR 24) from aqueous solutions was investigated.
SAC was characterized by iodine number, specific surface area, zeta potential, scanning electron
microscope and X-ray diffraction. Adsorption experiments were conducted as function of
particle size, SAC dosage, pH, salt concentration, contact time and initial concentration.
Desorption of dyes on SAC was studied in deionized water with different pH values and the dyeexhausted carbon was regenerated by thermal treatment. The results showed that the equilibrium
adsorption data were well represented by the Langmuir isotherm equation. The maximum
adsorption capacity (263.16 mg/g for MB and 34.36 mg/g for RR 24), high regeneration
efficiency and low cost (365 US$/t) of SAC provided strong evidence of the potential of SAC for
removing dyes from aqueous solutions [77].
Jae-Wook Lee et al.,(2006) studied the Submerged microfiltration membrane coupled
with alum coagulation/powdered activated carbon adsorption for complete decolorization of
reactive dyes. Even the presence of very low concentrations of dyes (1 mg L1) in the effluent is
highly visible and is considered aesthetically undesirable. It must be removed from wastewater
19

completely. This study systematically evaluates the performance of adsorption (three kinds of
powdered activated carbons), coagulation (AlCl36H2O) and membrane (submerged hollow
fiber microfiltration) processes individually in treating two kinds of reactive dyes (Orange 16
and Black 5) and then using a hybrid process with combined coagulationadsorptionmembrane
treatment system. Adsorption capacity and kinetics of Orange 16 were much higher and faster
than those of Black 5. The dye removal efficiency by coagulation was highly dependent on dye
concentration and solution pH. The hybrid process performance was far more superior that
individual process in removing both kinds of dyes. It was evident that the combined coagulation
adsorptionmembrane process has a great potential application for complete reactive dye
removal, production of high-quality treated water and allows the reduction in the use of
coagulant and adsorbent [78].
Sanja Papic et al., (2004) studied the removal of some reactive dyes from synthetic
wastewater by combined Al(III) coagulation/carbon adsorption process. This study was designed
to investigate the removal of reactive dyes, C.I. Reactive Red 45 and C.I. Reactive Green 8, from
wastewater using a two-step, Al(III) coagulation/activated carbon adsorption method. The effect
of pH and coagulant dosage as well as the effects of contact time and a powdered activated
carbon dosage on dye removal have been studied. The process was optimized with reasonable
consumption of coagulant and quantity of obtained sludge. Coagulation as a main treatment
process followed by adsorption achieved almost the total elimination of both dyes from
wastewater with significant reduction (90%) of chemical oxygen demand (COD), total organic
carbon (TOC) and adsorbable organic halide (AOX). Besides high efficiency of dye removal, the
combined treatment process offers many advantages for potential application such as coagulant
savings, minimal amount of sludge formation and also a economic feasibility since it does not
require high costs for chemicals and equipment [79].
Y.S. Al-Degs et al., (2011) studied the adsorption characteristics of reactive dyes in
columns of activated carbon. Adsorption behaviour of reactive dyes in fixed-bed adsorber was
evaluated in this work. The characteristics of mass transfer zone (MTZ), where adsorption in
column occurs, were affected by carbon bed depth and influent dye concentration. The working
lifetime (tx) of MTZ, the height of mass transfer zone (HMTZ), the rate of mass transfer zone
(RMTZ), and the column capacity at exhaustion (qcolumn) were estimated for the removal of
remazol reactive yellow and remazol reactive black by carbon adsorber. The results showed that
20

column capacity calculated at 90% of column exhaustion was lower than carbon capacity
obtained from equilibrium studies. This indicated that the capacity of activated carbon was not
fully utilized in the fixed-bed adsorber. The bed-depth service time model (BDST) was applied
for analysis of reactive yellow adsorption in the column. The adsorption capacity of reactive
yellow calculated at 50% breakthrough point (N0) was found to be 0.1 kg kg1 and this value is
equivalent to about 14% of the available carbon capacity. The results of this study indicated the
applicability of fixed-bed adsorber for removing remazol reactive yellow from solution [80].
Y. Al-Degs et al., (2000) studied the effect of carbon surface chemistry on the
removal of reactive dyes from textile effluent. The removal efficiency of activated carbon
Filtrasorb 400 (F-400) towards three highly used reactive dyes in the textile industry was
investigated. In this work, the adsorption capacities for the anionic reactive dyes, namely;
Remazol Reactive Yellow, Remazol Reactive Black and Remazol Reactive Red were
determined. The adsorption capacity data showed a high removal ability for the three reactive
dyes and a distinguished ability for R. Yellow. The high adsorption capacities for F-400 were
attributed to the net positive surface charge during the adsorption process. Surface acidity,
surface basicity, H+ and OH adsorption capacities and pHZPC for F-400 were estimated and
compared with other reported values [81].
Franciele Regina Furlan et al., (2010) studied the removal of reactive dyes from
aqueous solutions using combined coagulation/flocculation and adsorption on activated carbon.
The removal of two reactive dyes (Black 5 and Orange 16) was investigated. The objective of
this study was to investigate the removal of reactive dyes through a combined treatment process
with coagulation/adsorption on activated carbon. Activated carbon derived from coconut shells
was used as the adsorbent and aluminum chloride was used as the coagulant. In order to obtain
the best conditions for the removal of the dyes, the influence of the following parameters was
verified: coagulant and alkalizer dosage, aqueous solution pH, temperature of the mixture and
salt addition (sodium chloride). Spectrophotometry was the analysis technique used to measure
the concentration of dye remaining in the fluid phase. The results for the adsorption of the
reactive dyes were fitted to the models of the Langmuir, Freundlich and Radke-Prausnitz
isotherms and showed good correlation. The removal efficiencies were approximately 90% and
84% for the Black 5 and Orange 16, respectively. In order to evaluate the final effluent obtained
after the coagulation and adsorption process, acute toxicity tests were carried out with Artemia
21

salina and Daphnia magna, which verified that the effluent was atoxic. The combined
coagulation/adsorption process was shown to be an excellent option for the removal of reactive
dyes [82].
Mohd Azmier Ahmad et al., (2011) studied the optimization of rambutan peel based
activated carbon preparation conditions for Remazol Brilliant Blue R removal. The optimal
conditions for preparation of rambutan peel based activated carbon (RPAC) for removal of
Remazol Brilliant Blue R (RBBR) reactive dye from aqueous solution were investigated. The
RPAC was prepared using physiochemical activation method which consisted of potassium
hydroxide (KOH) treatment and carbon dioxide (CO2) gasification. The central composite
design (CCD) was used to determine the effects of the preparation variable, activation
temperature, activation time and KOH impregnation ratio on RBBR percentage removal and
RPAC yield. Two quadratic models were developed to correlate the preparation variables for
both responses. The significant factors on each experimental design response were identified
from the analysis of variance (ANOVA). The optimum conditions for RPAC preparation were
obtained by using activation temperature of 789 C, activation time of 1.8 h and IR of 3.5, which
resulted in 78.38% of RBBR removal and 18.02% of RPAC yield [83].
Tatiana Calvete et al., (2010) studied the application of carbon adsorbents prepared
from Brazilian-pine fruit shell for the removal of reactive orange 16 from aqueous solution:
Kinetic, equilibrium, and thermodynamic studies. Activated (AC-PW) and non-activated (C-PW)
carbonaceous materials were prepared from the Brazilian-pine fruit shell (Araucaria
angustifolia) and tested as adsorbents for the removal of reactive orange 16 dye (RO-16) from
aqueous effluents. The effects of shaking time, adsorbent dosage and pH on the adsorption
capacity were studied. RO-16 uptake was favorable at pH values ranging from 2.0 to 3.0 and
from 2.0 to 7.0 for C-PW and AC-PW, respectively. The contact time required to obtain the
equilibrium using C-PW and AC-PW as adsorbents was 5 and 4 h at 298 K, respectively. The
fractionary-order kinetic model provided the best fit to experimental data compared with other
models. Equilibrium data were better fit to the Sips isotherm model using C-PW and AC-PW as
adsorbents. The enthalpy and entropy of adsorption of RO-16 were obtained from adsorption
experiments ranging from 298 to 323 K [84].

22

Alvin W.M. Ip et al., (2010) investigate the kinetics and mechanisms of removal of
Reactive Black 5 by adsorption onto activated carbons and bone char.The adsorption of a large
reactive dye, Reactive Black 5, onto four adsorbents has been studied. A commercial active
carbon, F400, was selected as a standard and two active carbons prepared from bamboo, a
biomaterial. The two bamboo derived carbons, BACX2 and BACX6 had high specific surface
areas, namely, 2123 and 1400 m2/g, respectively. A fourth widely used adsorbent, bone char,
was also tested. The adsorption capacities for F400, bone char, BACX2 and BACX6 were 198,
160, 286 and 473 mg/g, respectively. A series of batch kinetics were carried out to investigate
the rate and possible mechanism of Reactive Black 5 adsorption. Two pseudo-kinetic models and
one intraparticle diffusion model were tested. The experimental concentration versus time decay
curves were best explained by the intraparticle diffusion model [85].
.

Hyun-Doc Choi et al., (2008) studied the removal characteristics of reactive black 5

using surfactant-modified activated carbon. Reactive dyes are non-degradable and toxic to
environments and human being, and their solutions have some color even after wastewater
treatment. To remove toxic dyes, adsorption is common choice. In this study, to improve the
adsorption capacity, the effect of cationic surfactant was studied to remove reactive black 5
(RB5) by activated carbon (AC) using cetylpyridinium chloride (CPC). Three different ACs
were studied; pure AC, AC in CPC solution and precoated AC by CPC. Regardless of surfactant
presence, the sorption kinetics followed pseudo-second-order kinetic model. Equilibrium
adsorption capacities were determined by fittings experimental data to three well-known
isotherm models; Langmuir, Freundlich and double scheme of Langmuir model. A double
scheme of Langmuir model was more proper to explain experimental data than the conventional
Langmuir and Freundlich model. Cationic surfactant could enhance sorption capacity of RB5 on
activated carbon, and the extent of enhancement is highly dependent on pore size distribution of
activated carbon [86].
Dilek Angn et al., (2013) studied the production and characterization of activated
carbon prepared from safflower seed cake biochar and its ability to absorb reactive dyestuff. The
use of activated carbon obtained from biochar for the removal of reactive dyestuff from aqueous
solutions at various contact times, pHs and temperatures was investigated. The biochar was
chemically modified with potassium hydroxide. The surface area and micropore volume of
activated carbon was 1277 m2/g and 0.4952 cm3/g, respectively. The surface characterization of
23

both biochar and activated carbon was undertaken using by Fourier transform infrared
spectroscopy and scanning electron microscopy. The experimental data indicated that the
adsorption isotherms are well described by the DubininRadushkevich (DR) isotherm equation.
The adsorption kinetics of reactive dyestuff obeys the pseudo second-order kinetic model. The
thermodynamic parameters such as G , H

and S

were calculated to estimate the nature

of adsorption. The activation energy of the system was calculated as 1.12 kJ/mol. According to
these results, prepared activated carbon could be used as a low-cost adsorbent to compare with
the commercial activated carbon for the removal reactive dyestuff from wastewater [87].

24

Table 2.1: Removal of reactive dye using different adsorbents.

Adsorbate

Adsorbent

Results/conclusion

Refrence

Reactive

Clay

The removal efficiencies of synthetic talc

[88].

Procion

Adsorbents

stable above 80% until the initial dye

Dyes

concentration reached at 160 mg.L-1 of

both reactive procion dyes when the
liquid/solid ratio of 50 mL.g-1. Synthetic
talc and kaolin showed higher adsorption
capacity under acidic condition because of
higher zeta potential.

Reactive

Quaternary

Adsorption was shown to be independent of

orange 16

chitosan salt

solution pH. The experimental data best

[89].

fitted the pseudo-second-order model. The

adsorption rate was dependent on dye
concentration
adsorbent.
capacity

at

The

the

surface

maximum

determined

was

of

the

adsorption
1060 mg

of

reactive dye per gram of adsorbent,

corresponding to 75% occupation of the
adsorption sites.
Reactive
Blue

Calcined
114 alunite.

Acidic pH was favorable for the adsorption

of RB114 and alkaline pH was favorable to

(RB114),

both RY64 and RR124. The adsorption

Reactive

capacities were found to be 170.7, 236 and

Yellow

64

153 mg dye per gram of calcined alunite for

(RY64) and

RB114, RY64 and RR124, respectively.

Reactive

The experimental data were fitted by the

Red
(RR124)

124

second-order kinetic model, which indicates

that chemicalsorption is the rate limiting
step, inside of mass transfer
25

[90].

Reactive

Modified silk Adsorption depended on solution pH, dye

blue MR

cotton hull

[91]

concentration, carbon concentration and

contact time. Equilibrium was attained with
in 60 min. The adsorption capacity was
found to be 12.9 mg/g at an initial pH of
2 0.2 for the particle size of 125250 m
at room temperature (30 2 C).

Naphthol

Mesoporous

The

maximum

adsorption

capacities

Blue Black, carbon

obtained for the dyes were: 270 mg/g for

NBB;

Naphthol

(MCSG60)

Reactive

Blue

Black;

270 mg/g

for

Reactive Black 5 and 280 mg/g for Remazol

Black

5,

Brilliant Blue. Further batch experiments

RB5;

and

showed Mesoporous carbon (MCSG60)

Remazol

successfully adsorbed the dyes over a wide

Brilliant

pH

Blue

[92].

R,

range

and

at

low

adsorbate

concentration.

RBBR
Reactive

Porous MgO Experimental results indicate that the

blue 19 and powder

prepared MgO powder can remove more

reactive red

than 98% of both dyes under optimum

198

operational conditions of a dosage of 0.2 g,

[93].

pH 8 and a contact time of 5 min for initial

dye concentrations of 50300 mg/L. The
maximum predicted adsorption capacities
were 166.7 and 123.5 mg of dye per gram
of adsorbent for RB 19 and RR 198,
respectively.
Reactive

Material

The adsorption evaluation of the composite

Black 5 dye

consisted

of material presented high adsorption capacity

cross-linked

(277 mg/g at 25 C).

chitosan (CH)
26

[94].

and

graphite

oxide (GO)
Methylene

Sludge

With the solution pH increase, the MB [95].

Blue (MB) (collected

and

from

Reactive

biological

Red

uptake increased; whereas the RR4 uptake

a decreased. The maximum uptake of RR4 by

4 coke

(RR4)

wastewater

protonated sludge was 73.7 mg/g at pH 1,

and the maximum uptake of MB by sludge
was 235.3 mg/g at pH 9.

treatment
plant)
Reactive
textile

Industrial

Dye adsorption equilibrium isotherms were [96].

dye waste sludge determined at 25 and 35 C and pH of 4, 7

(Remazol

mainly

and

10

revealing

reasonably

fits

to

Brilliant

composed by Langmuir and Freundlich models. At 25 C

Blue)

metal

and pH 7, Langmuir fit indicates a

hydroxides

maximum adsorption capacity of 91.0 mg/g.

A pseudo-second-order model showed good
agreement with experimental data.

Reactive

Chitosan-

The adsorption behavior of Chitosan- [97].

dye

modified

modified palygorskite showed that the

palygorskite

adsorption kinetics and isotherms were in

good agreement with the pseudo-secondorder equation and the Langmuir equation,
and the maximum adsorption capacity of
Chitosan-modified palygorskite calculated
by the Langmuir model was 71.38 mg g 1,
which was much higher than that of the
unmodified palygorskite (6.3 mg g 1).

Reactive

Nanoparticles

blue 5

of delafossite- adsorption properties towards reactive dye,

type

The nanoparticles showed the excellent [98].

reactive blue 5 (RB5). The kinetic studies
27

LiCo0.5Fe0.5

indicate that the removal process obeys the

O2

second-order kinetic equation. Also, the

isotherm

evaluations

reveal

that

the

adsorption of reactive blue 5 by the

nanoparticles follows the Freundlich model.
Congo Red Sludge

The adsorption is highly pH dependent due [99].

(anionic

generated

in to

formation

reactive

removal

of hydroxylated

dye).

heavy

of

various

species.

The

charged
maximum

metal adsorption capacity (qm) increases from

by

271 to 513 mg/g when the initial pH is

electrocoagula adjusted to 3.0 instead of 10.4. Preferable

tion.

fitting

of

Langmuir

isotherm

over

Freundlich isotherm suggests monolayer

coverage of adsorbate at the surface of
adsorbent.
Reactive
Red

Spirulina

The maximum adsorption capacities of

120 platensis micr

reactive red-120 dye were found at pH 2

(RR-120)

oalgae

[100].

(SP) and 298 K, and the values were 482.2 and

and

267.2 mg g1 for

the

commercial

platensis microalgae and activated carbon

activated

adsorbents,

carbon (AC)

efficiency of Spirulina platensis microalgae

respectively.%

Spirulina
removal

and commercial activated carbon was 94.4

99.0% and 93.697.7% respectively.
Reactive

Sunflower

Sunflower seed shells led to a percentage of

Black

5 seed

shells dye removal higher than mandarin peelings

(RB5)

(SS)

and (85% and 71% after 210 min, respectively,

mandarin

for an initial reactive black 5 concentration

peelings (MP)

of 50 mg L1 and an initial pH of 2.0). On

the whole, the results in this study indicated
that SS were very attractive materials for
28

[101].

removing anionic dyes from dyed effluents.

The rate of adsorption followed a pseudosecond-order kinetic model.
Reactive
Red

Adsorbent

The optimum pH, temperature, particle size [102].

and prepared

by and time were found to be 10.8, 59.25 C,

Acid Brown pyrolysing

dye

a 0.0525 mm and 395 min, respectively, for

mixture
carbon

of Reactive Red 3GL and those for Acid

and Brown 29 were 1.4, 27.5 C, 0.0515 mm

flyash at 1:1 and

ratio

285 min,

respectively.

Complete

removal (100%) was observed for both the

dyes using the hybrid adsorbent.

Reactive
Red

Jatropha

The

120 curcas shells

(RR-120)

in

maximum

sorption

capacity

for

adsorption of the dye occurred at 323 K,

natural attaining

values

of

40.94

and

form (JN) and 65.63 mg g1 for JN and JP, respectively.

treated

by % removal was obseved 68.2% and 94.6%,

non-thermal
plasma
biosorbents

for Jatropha curcas shells in natural form

as and Jatropha curcas shells
treated by non-thermal plasma, respectively.

(JP).

29

[103].

3. MATERIALS AND METHODS

3.1 Waste water

Aqueous solution of CBSOL Red LE wool dye was taken as waste water. Initially 100
mg/l of stock solution was prepared which was diluted to make the working solution to suit the
feasibility of experiments.
3.2 Analytical Methods
The determination of the concentration of reactive CBSOL Red LE wool dye was
performed by finding out the absorbance characteristic wavelength using UV/VIS
spectrophotometer (Perkin Elmer, Schimadzu, Japan). A solution of known concentration was
taken and the absorbance was determined at different wavelengths to obtain a plot of
absorbance versus wavelength. The wavelength corresponding to maximum absorbance (max)
was determined. The max for reactive CBSOL Red LE wool dye solution was found to be 504
nm. Calibration curve was plotted between the absorbance and the concentration of reactive
CBSOL Red LE wool dye solution (Figure: 3.1).

0.35
y = 0.0124x
R = 0.9974

0.3

Absorbance

0.25
0.2
0.15
0.1
0.05
0
0

10

15

20

25

30

Dye Concentration (mg/L)

Figure 3.1: calibration curve between the absorbance and the concentration of reactive
CBSOL Red LE wool dye solution.

30

3.3 Experimental Programme

For each experiment, a known amount of the adsorbent was introduced into 250 ml
stoppard conical flasks in which 100 ml of the reactive CBSOL Red LE wool dye solution of
known pH was already present. This was kept in a temperature controlled shaker at a constant
speed of 150 rpm at a pre-decided constant temperature for 7 hour to attain the equilibrium. The
adsorbent and adsorbate were separated from the reactive CBSOL Red LE wool dye solution
after 7 hour and analyzed for concentration. The percentage removal efficiency and adsorption
capacity of reactive CBSOL Red LE wool dye aqueous solution was calculated using the
following relationship:

Removal efficiency, R =

100

(3.1)

Adsorption capacity, qt =

x100

(3.2)

Where,
Ci is initial reactive CBSOL Red LE wool dye aqueous solution concentration, Cf is the
equilibrium reactive CBSOL Red LE wool dye aqueous solution concentration (mg/l), Cj =
activated carbon loading (adsorbent dosage), g/100ml and qt = amount of dye adsorbed per unit
weight of activated carbon.

3.4. Kinetics of adsorption: Pseudo-first-order and pseudo-second-order models were used to

calculate the kinetic parameters at various Ci values (50-100 mg/l). Optimum adsorbate dose of
Activated carbon was used. The amount of adsorbate adsorbed, qt (mg/g), at any time t was
calculated as:
qt =

(C i C t )
m

(3.3)

Where, Ct is the Red LE Dye concentration (mg/l) at time t, V is the volume of the
solution (litre).
31

The adsorption of adsorbate from solution to adsorbent can be considered as a reversible

process with equilibrium being established between the solution and the adsorbate. Since, nondissociating molecular adsorption of adsorbate molecules on adsorbent was assumed; the
sorption phenomenon can be described as the diffusion controlled process.
Using first order kinetics it can be shown that with no adsorbate initially present on the
adsorbent, the uptake of the adsorbate by the adsorbent at any instant t is given as:

qt = qe 1 exp( k f t )

(3.4)

where, qe is the amount of the adsorbate adsorbed on the adsorbent under equilibrium
condition, kf is the pseudo-first order rate constant.
The pseudo second-order adsorption kinetic rate equation is expressed by the integrated equation
after using the boundary conditions as:

qt =

tk S qe2
1 + tk S qe

(3.5)

Marquardts percent standard deviation (MPSD [104] was used to find out the error function to
represent the experimental data.
This error function is given as:

1
MPSD = 100
nm n p

qt ,i ,exp qt ,i ,cal

qt ,i ,exp
i =1

(3.6)

In this equation, the subscript exp and cal represent the experimental and calculated
values, n m is the number of measurements, and np is the number of parameters in the model.

32

4. RESULTS AND DISCUSSION

4.1 Adsorption experiments

The % dye removal efficiency and adsorption capacity was determined from the dye
concentration in the solution before and after adsorption with activated carbon. Effect of
activated carbon dosage, pH of reactive dye solution and time on the removal efficiency and
adsorption capacity was studied using different activated carbon dosage, pH of reactive dye
solution and time (Saran et al., 2013) [105]. The optimum values of operational parameters were
found to be m = 2.92 g/100 ml, t = 6.75 h and pH = 3.95 (Saran et al., 2013) [105]. At these
operational parameters, kinetics and isothermal study were conducted.

4.2Adsorption Kinetics
Pseudo-first-order and pseudo-second-order kinetic models used to examine their validity
with the experimental kinetic adsorption data. The best-fit values of the model parameters,
correlation coefficients and MPSD values are given in Table 4.1.
It may be concluded that pseudo second-order kinetic model with non-linear regression
best fits the adsorption kinetics. The fitting of pseudo second-order and pseudo first-order model
with kinetic experimental data is shown in Fig. 4.1.
From Table 4.1, it is observed that the qe and ks values were found to be increase with an
increase in Ci. The uptake rate is limited by the Ci of Red LE Dye and the Red LE Dye affinity to
the adsorbent, diffusion coefficient of the Red LE Dye in the bulk and solid phases, The increase
in Ci of Red LE Dye also enhances the interaction between Red LE Dye and the adsorbent. The
rate of adsorption also increases with the increase in Ci due to increase in the driving force.

33

Table 4.1 Best-fit values of the model parameters

Pseudo-first-order model
Ci

qe,exp

qe,cal

(mg/l)

(mg/g)

{mg/g)

kf
(min-1)

R2

MPSD

(non-linear)

100

2.832

2.565

0.035

0.97

31.34

50

1.462

1.397

0.021

0.98

21.65

Pseudo-second-order model
ks

qe,exp

(mg/l)

(mg/g)

MPSD

100

2.780

0.018

0.137

0.99

17.60

50

1.647

0.012

0.033

0.99

17.77

(g/mg min) (mg/g min) (non-linear)

34

R2

Ci

Ci (mg/l)
100 mg/l
100 cal F
50 cal S

qt (mg/g)

100, cal S
50 mg/l
50 cal F

0
0

100

200

300

400

500

Time (min)
Fig.4.1 Kinetics of CBSOL red LE dye on activated carbon. (Experimental results are
shown by data points, Solid line shows pseudo second-order kinetic model fitting, and
dotted line shows pseudo first-order kinetic model)

35

5. CONCLUSIONS
On the basis of the results and discussion presented for the removal of CBSOL Red LE
Wool dye from aqueous solution by adsorption process with activated carbon, following
conclusion can be drawn.
1. qe and ks value increases with increase in Ci.
2. The uptake rate is limited by the Ci of Dye.
3. The rate of adsorption increases with increases with increases in Ci.
4. Psuedo second-order was found to best for Equilibrium Data.

36

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