for dyes

1. Thermodynamic and kinetic studies for
the removal of Safranin dye from
aqueous solution
using NaP zeolite synthesized from
Coal fly ash
Supervisor Presented By
Dr. M. K. Dwivedi Payal jain
Govt. Holkar science college indore

2. Introduction
• A large number of dyes are produced annually and used in various industries like textiles, cosmetics,
paper, leather, pharmaceuticals and food. In textile industry, process of dyeing and printing colored
products contaminated wastewater with dyes. Discharge of contaminated wastewater without further
treatment can seriously damage the environment [1].
• Possible methods of removal of dyes from wastewaters include chemical oxidation, froth flotation,
adsorption, coagulation, electro-dialysis, cloud point extraction etc. Among these, adsorption offers the
best potential for overall treatment, and it can be expected to be useful for a wide range of compounds,
more so than any of the other listed processes [2,3].
• Adsorption process has proved highly effective for organic material like dyes from wastewater, a
treatment that can economically meet current effluent standards and water reuse requirements [4].
• The adsorbents are mainly derived from sources such as natural zeolite, coal, clay, ores and other waste
resources. The adsorbents prepared from the waste resources used include petroleum wastes, sawdust,
fertilizer waste, sugar industry wastes, coconut shell tannin-rich materials, blast furnace slag, chitosan and
seafood residues, seaweed, algae, scrap tyres, fruit wastes and peat moss [5, 6].
• Commercial activated carbon is the most widely used as adsorbent material in the dyes removal [7, 8].
Many natural materials were used as natural low cost adsorbents for the removal of dyes from wastewater
such as orange peel [9], rice husk [10], fly ash [11], papaya leaf [12], natural zeolite [13], chitosan films
[14], calotropis gigantea [15], novel nonconventional activated carbon [16], peanut shell powder [17],
cow dung ash [18], agricultural waste [19], sugar can stalks [20], modified pumice stone [21] and sugar
cane bagasse [22].

3. Introduction continued…
• Safranin is an azine dye which are amongst the oldest and most commonly known
synthetic dyes. It’s water-soluble nature and intense reddish-brown color facilitates its use
as food dye in flavoring and coloring cookies and candies. It is also used in dyeing of
tannin, cotton, bast fibers, wool, silk, bast fibers, leather and paper. Due to its extensive
use as colorant in food and textile industries it has been considered as the bulk dyes that is
discarded as effluents from the textile and food industries. An exposure to this, causes
irritation to respiratory systems, skin, as well as digestive tract infections when ingested
[23, 24]. Safranin has been considered as the model compound to speak to the colours that
are delivered in effluents from the material and food ventures, it is also used as a colorant.
Introduction to these effluents might be disturbing to respiratory frameworks, skin, and
stomach related lot contaminations when ingested [25, 26].
• There are seven thermal power stations in Madhya Pradesh, India which discharge
11.4186 million tons of fly ash every year. Out of it, only 4.1064 (35.96 %) million tons
of fly ash utilized per year. In Madhya Pradesh 64.04 % of fly ash remaining unutilized
per year according to Central Electricity Authority Thermal Civil Design Division 2016-
17 [27]. Fly ash and bottom ash contain silicon in abundance therefore these raw
materials have been utilized for the production of mesoporous silica [28]. In spite of the
good work, the adsorption ability of fly ash required to be further enhanced for the useful
application in industry.

4. Introduction continued
• The present investigation has been taken to carry out the hydrothermal synthesis
of zeolite from coal fly ash which has many advantages compared with the other
methods in order to establish a more effective and environmentally friendly
method for the treatment of coal fly ash and see its utility in the removal of
Safranin dye from aqueous solution.
Structure of safranin

5. Material and method
• Material:Coal fly ash was collected from H.E.G. Thermal Power Station, Mandideep, Bhopal,
India.
• Adsorbate:A stock solution 1000 ml was prepared by dissolving a weighed amount (1.0g) of
safranin in one-liter distilled water. Different concentrations were prepared by diluting the stock
solution with suitable volume of distilled water and the natural pH of the stock solution was around
5.6.
• Zeolite synthesis:NaOH is added with coal fly ash in different ratios of 1:2, 1:1.5 and 1:1.2 and
kept for fusion at varying temperatures of 350oC, 450oC and 550oC for 12 hours. fusion mixtures
were washed dried at 110oC for 12 hours.
• Instumentation: UV-Visible spectrophotometer (Systronic, Model No. 104).

6. RESULT AND DISCUSSION
Table 1: Characterization of Fly ash and Zeolite
Constituents SiO2 Al2O3 Fe2O3 CaO TiO2 K2O P2O5 SO3 Na2O MgO LOI
CFA Wt% 55.26 22.75 7.12 4.1 2.95 2.14 1.65 1.58 1.23 0.63 4.1
CFA:NaOH Wt% 49.13 17.43 7.06 3.8 2.89 2.04 1.57 1.53 6.19 0.61 -----
FTIR spectra of (a) Coal fly ash (b) Alkali activated coal fly ash
FTIR analysis

7. SEM analysis
SEM analysis of (a) Untreated CFA, (b) CFA:NaOH (1:1.2), (c)
CFA:NaOH (1:1.5) and (d) CFA:NaOH (1:2)
a b
C d

8. XRD analysis
XRD analysis of (a) Coal fly ash, (b) CFA: NaOH (1:1.2), (c) CFA:NaOH (1:1.5) and (d) CFA:NaOH (1:2) at 550oC
a b
c d

9. Adsorption studies
Effect of contact time , Effect of pH, Effect of adsorbent dose
0
20
40
60
80
0 50 100 150 200 250
%
Adsorption
Time (min)
5ppm
10ppm
20 ppm
40
50
60
70
80
90
100
4 5 6 7 8 9 10 11 12
%
Adsorption
pH
0
20
40
60
80
100
0 5 10 15 20 25 30
%
Adsorption
Amount of adsorbent (g/l)
5 ppm
10ppm
15ppm
Influence of contact time on uptake of Safranin dye Influence of pH on uptake of Safranin dye
Influence of adsorbent dose on uptake of Safranin dye

10. Adsorption isotherm
Langmuir isotherm plot of Safranin dye Freundlich isotherm plot of Safranin dye
Temkin Isotherm plot of Safranin dye D-R plot of Safranin dye

11. TABLE 2. Langmuir, Freundlich, Temkin, Dubinin-Radushkevich isotherm parameters at 298 K
S. No. Isotherm Model Parameters Value R2
1.
Langmuir
b
qm (mg/g)
RL
1.0687
7.14
0.16
0.9790
2. Freundlich
Kf (mg/g)
1/n
3.790
0.758
0.9820
3.
4.
Temkin
Dubinin
Radushkevich
B (J/mole)
AT (L/mg)
bt
qDR (mg/g)
B (mol g-1L)2
E (KJ mol-1)
2.173
6.487
2.173
8.715
9×10-8
2.357
0.9000
0.9590

12. Kinetic Studies
Elovich plot of Safranin dye Intra particle diffusion plot of Safranin dye
Legergren plot of Safranin dye Pseudo second order plot of Safranin dye

13. TABLE 3. Kinetic Model Parameters
S. No. Isotherm Model Parameters Value R2
1.
Pseudo First Order
kad (min-1)
qe (mg/g)
1.6 X 10-2
0.037
0.9910
2. Pseudo Second Order
K2 (g/mg)
qe (mg/g)
1.726
0.973
0.9990
3.
4.
Intra- particle diffusion
Elovich Kinetics
Kad
C
α (mg/g)
β (g/mg)
0.003
0.932
9.45 X 1030
83.33
0.9635
0.9876

14. CONCLUSION
• Zeolite was prepared from coal fly ash with sodium hydroxide in different concentration ratios
at 550 °C with activation time of 12 hours by direct hydrothermal method. It was characterized
by XRF, SEM, XRD and FTIR.
• Batch studies revealed that the removal of Safranin dye was strongly pH dependent and
maximum dye removal of 97.14% was observed at 10 mg/l dose of adsorbate at equilibrium
pH of 9.0, optimum adsorbent dose and contact time were found to be 5 g/l and 180 minutes
respectively.
• It was found that adsorption increased with rise in temperature thereby showing the process
exothermic in nature.
• The adsorption data was analyzed by Langmuir and Freundlich models and fitted well. The
fitness of Langmuir’s model indicated the formation of monolayer coverage of the adsorbate
on the outer surface of the adsorbent.
• The characteristic parameter and mechanism of adsorption were also investigated using
isotherms and kinetic models. The adsorption data reflected best fits in the following order
based on coefficient of determination: Freundlich > Langmuir > Dubinin Radushkevich >
Temkin.
• The adsorption data obeyed Pseudo-second order > pseudo first order > Elovich > Intra
particle diffusion. The developed adsorbent is quite cheaper than commercially available
activated carbon, while their performance is comparable.

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