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Kul, Benek, Selçuk, and Onursal, JOTCSA. 2017; 4(2): 525-536. RESEARCH ARTICLE
525
Using Natural Stone Pumice in Van Region on Adsorption of Some
Textile Dyes
Ali Rıza KUL
1*
, Veysel BENEK
1
, Ahmet SELÇUK
2
, Nilgün ONURSAL
3
1
Science Faculty of Yuzuncu Yil University, 65300, Van, Turkey
2
Faculty of Education Yuzuncu Yil University, 65300, Van, Turkey
3
Faculty of Education of Siirt University, 56100, Siirt, Turkey
Abstract: Toxic effect of textile dyes their increasing quantities in air, soil and water
environments, because of growing of industrial activities, they must be taken into
consideration since they give harm to the environment. We come across textile dyes in
natural wetlands as result of uncontrolled industrial wastes. Textile dyes that can
accumulate easily in their environments may show toxic effects. Pumice, accruing as a
result of volcanic events and durable against chemical factors, is a rock that has porous
structure. Pumices have a porous structure because of sudden cooling of the rock and
sudden leaving of gases a result of volcanic events. Thanks to these pores, pumices’ heat
and sound insulation are quite high. The most distinctive feature of pumice from other
rocks is that it has different colors and there is not crystal water in its porous structure.
Adsorption studies are applied with Van Pumice at pH = 6, the adsorption mechanism and
changing dye concentration. As result of these researches, it has been found out that there
are different adsorption movements at pH 6 between Neutral Red and Van Pumice. The
result of this study shows that the Pumice found in Lake Van gives a better fit for the
Langmuir Isotherm (model) and the amount of adsorption increases with the temperature.
We thereby conclude that the Pumice located in Lake Van is a recommended adsorbent for
filtering the used textile dye in aqueous medium.
Keywords: Textile dyes; adsorption; isotherm; Van pumice; thermodynamics.
Cite this: Kul A, Benek V, Selcuk A, Onursal N. Using Natural Stone Pumice in Van Region
on Adsorption of Some Textile Dyes. JOTCSA. 2017;4(2):49–60.
DOI: 10.18596/jotcsa.292662.
Corresponding author. E-mail: alirizakul@yyu.edu.tr.
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526
INTRODUCTION
Pumice is a glassy, porous, and volcanic rock which occurs with the result of hollow,
spongy, volcanic rocks and is resistant against the physical and chemical effects (22). The
name "Ponza" or "Pomza" comes from Italian. There are different names in different
languages. In French it is called as "Ponce", in English, the middle ones are "Pumice",
naturally the tiny ones are "Pumicite", In German, the big ones are called as "Bimstein",
and tiny ones are called as "Bims". In Turkish, it is known as "Sünger taşı", "Köpük taşı",
"Topuktaşı" (6).
Because pumice it mostly porous, its heat and sound insulation is quite high. According to
Mohs scale, its hardness is 5-6. It does not contain crystal water. Its chemical component;
60%-70% SiO
2
, 13%-15% Al
2
O
3
, 1%-4% Fe
2
O
3
, 1%-2% CaO, 1%-2% MgO, 2%-5% Na
2
O,
3%-4% K
2
O and it contains TiO
2
, SO
3
and Cl (13, 24).
During formation, because of sudden cooling and the gases inside the pumice's leaving, it
contains countless pores from macro scale to micro scale. Between pores are generally
(especially micro ones) disconnected hollows. Pores on pumice are mostly not connected
to each other. Each pore is isolated from each other with a glassy membrane. Because of
this feature, pumice is a good adsorbent (24, 3).
Pores on pumice are smaller than 1 mm. Pores are irregular, spherical, round and like
elongated pipes (11, 2).
The more pumice's piece size increases the more porous percent increases. Pumice’s
excess of porous percent and low specific weight ensure it to be used as a pouring material
for insulation areas. Also, thanks to the same features, it is highly porous; Pumice pieces
are not too much resistant. However, its durability is suitable for rock durability which was
used in carrier wall construction. (To 6 floors). Pumice is a good heat insulator. This feature
is increased with the event, which is called as “stack Porousness", in pumice block
manufacture that is especially struggled to reach. For the stack porousness, concrete is
prepared with a quite thin mortar and is ensured to cover only surround of pumice pieces
in a thin manner. The Pumice pores are not only helpful for insulation but also pumice
structure elements are highly adsorbent because it has features of removing capillary.
Pumice is grinded easily because of being a volcanic glass. Granulated Pumice was used
for similar goals both for the purpose of polishing and stoning and in match factories as an
ignition material and filling material, soap and cosmetic industry (21, 26).
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Because of porous being disconnected and having spaces, pumice is light, it can swim for
a long time and its permeability is low and its insulation (heat – sound insulation) is quite
high. Chemically, it contains about 75% silica. The amount of SiO
2
that rock contains,
provides an abrasive feature to the rock, therefore, it reveals a chemical status that can
easily erode steel. The compound of Al
2
O
3
provides a high resistant to fire and heat. Na
2
O
and K
2
O are known as minerals which give reactions in textile industry (9).
Economically functioned reserves are generally after tertiary reserves. World's pumice
reserves are more than 16 billion tonnes. USA has the biggest reserves while Turkey is the
second in terms of total pumice reserves. Important reserves of Turkey are in Tatvan and
Ahlat, Niğde-Nevşehir, Iğdır and Kars, Mollakasım (Van), Erciş (Van), Güdül (Ankara),
Doğubeyazıt (Ağrı) and Cumaovası' (İzmir).
Main manufacturers are Italy, Greece, Spain, Turkey, France, and Germany (26, 8).
Pumice rocks have recently gained updating as a popular industrial row material parallel
to various industries' establishment and development. Pumice was used in a large area
mainly as a light structure material, cement production, and filter material, acoustic and
polishing in industry. However, in our country, it is mostly used in bleaching jeans and in
production of briquette as a light structural material (24, 16).
Coloring of objects is expressed as "dyeing". Dye was used to protect the surface of objects
from external influences and to give a nice view. In speech, dye and dye material words
are used in the place of each other. These two words are not synonyms. Dyes are generally
inorganic. They are mixtures, which are mixed with a connector but dissolved in the
medium. They can be removed by scoping in large forms.
The materials which are used to color fabric and fiber are called as "dyeing material"
However, all colorful materials or color giving materials are not dye materials. Coloring,
applied by dye materials are not similar to coloring, applied by dye. Coloring is generally
applied with various dye methods in the form of solution or suspension.
All dye materials are organic compounds. The material to be dyed changes its structure by
chemical interaction with the dye. For this reason, the applicant cannot bring the material
back to the original by washing or cleaning. For that reason, the first dyes that are used
are mixture of metal–oxide, clay and some plant's sap (19).
Kul, Benek, Selçuk, and Onursal, JOTCSA. 2017; 4(2): 525-536. RESEARCH ARTICLE
528
Fe
2
O
3
, Cr
2
O
3
, Pb
3
O
4
, HgS, graphite can be given as examples for the natural inorganic dyes.
Some of the dye materials are from natural sources, and some of them are synthetic.
Natural dye materials can be obtained generally from skin of animals and glands, root,
shell, seed, and fruit of plants and from microorganisms like yeast bacteria in the result of
simple chemical applications (4).
In the textile industry, one of the main problems is the removal of dyes and pigments from
the wastewater. It is known that most dyes are toxic, carcinogenic, and mutagenic to
aquatic organisms, so they have to be removed. Several methods, such as filtration,
coagulation, chemical oxidation, adsorption, etc., are used in order to remove dyes from
wastewater (18, 23, 9).
One of our aims is to evaluate pumice of the local resource, Van (Turkey), the original
material for production of adsorbent. Besides, it is known that pumice has pores. The
second purpose of this study is to investigate the adsorption isotherm, kinetics and the
thermodynamic parameters adsorption onto pumice derived from the Van region.
MATERIALS AND METHODS
Chemical Materials: Experimental data are obtained from pH=6 solution. Different
concentrations of dye material's solution (50 ppm, 60 ppm, 70 ppm) are prepared for the
experiment.
Adsorbents: Van Pumice was used as an adsorbent during experiment. Chemical
component of this pumice given in Table 1.
Table 1. Chemical components of Van pumice.
Van
Pumice
SiO
2
Al
2
O
3
Fe
2
O
3
CaO MgO K
2
O Na
2
O SO
3
Loss of
Combustion
69.00
14.65
2.51
1.11
0.55
3.520
2.48
0.40
4.76
Method: In this study, Van Pumice was used whose chemical analysis results are given.
Adsorption studies were applied with Van Pumice.
Pumices were applied the following operations detailed below:
a) Washing stage: Van Pumice which was grinded in the mill and which was filtered from
230 mesh sieve, was dried for 5.5 hours in the oven. 100 grams of Van Pumice was mixed
12 hours with 1.7 liter of pure water in the mixer. After mixing stage was finished, the
material was kept idle for 12 hours. It was observed that aqueous phase and solid phase
Kul, Benek, Selçuk, and Onursal, JOTCSA. 2017; 4(2): 525-536. RESEARCH ARTICLE
529
were separated. Solid phase was separated by filtering. Solid phase was kept at ambient
conditions for 168 hours to dry. Dried Van pumice was filtered again with 230 mesh sieve.
It was placed in a desiccator until the time of experiment. Van Pumice was grinded in the
mill. After that, the size of the piece was minimized by filtrating 230 mesh sieves.
In the studies of adsorption balance, 1 gram of Pumice was treated 500 mL of dye material
solution. Dyeing material solutions were prepared in 50, 60, and 70 ppm concentrations,
were shaken with Van Pumice at different times (2, 5, 10, 15, 20, 25, 30, 40, 50, 60, 70,
80, 90, 100, 120, 150, and 180 minutes) in 25
0
C, 35
0
C, 45
0
C temperatures.
Dyeing material adsorption was examined depending on heat and time in the example of
Van Pumice. All of the adsorption measurement was applied with a spectrophotometer
(T80+ UV/VIS).
RESULTS AND DISCUSSION
Freundlich Isotherm
The Freundlich isotherm assumes an empirical equation based on the heterogeneous
surface of adsorbent. The linear form of the Freundlich isotherm is expressed as (15):
logq
e
= logK
f
+ nlogC
e
(1)
where K
f
is the Freundlich coefficient related to adsorption capacity, and n relates to
adsorption intensity. The values of the Freundlich constants were obtained from the linear
correlations between the values of log q
e
and log C
e
. In the Freundlich adsorption constant,
n should be greater than 1.
Langmuir Isotherm
In the solid/liquid adsorption process, adsorption of the solute is usually characterized by
either mass transfer (boundary layer diffusion) or intraparticle diffusion or even both (12).
The adsorption data of dye removal from pumice was analyzed by the Freundlich and
Langmuir isotherm models. The Langmuir isotherm model is valid for monolayer
adsorption. The linear equation of the Langmuir isotherm is (10):
=
ଵ
×
+
ଵ
ܥ
(2)
where, C
e
is the equilibrium concentration of dye in the solution, q
e
amount of dye adsorbed
at equilibrium, q
m
Langmuir adsorption capacity, and b Langmuir constant.
The values of the Langmuir constants and coefficient determination R
2
are given in Table
2. The Langmuir adsorption capacity (q
m
) was found to be 27.3393, 26.5741 and 23.8115
mg/g at different temperatures (298, 308 and 318 K).
Kul, Benek, Selçuk, and Onursal, JOTCSA. 2017; 4(2): 525-536. RESEARCH ARTICLE
530
Table 2. Equal values of Neutral Red adsorption on Langmuir and Freundlich equals from
different temperature.
T (K)
Langmuir
Freundlich
b (L/mg)
q
m
(mg/g)
R
2
n
K
f
(mg/g)
R
2
298
1,2921
27,3393
0,9997
3,7312
2,5977
0,9997
308
1,0537
26,5741
0,9971
10,0387
3,5430
0,9299
318
1,0209
23,8115
0,9990
34,4567
3,7676
0,7050
When R
2
values of both two adsorption isotherm models are taken into consideration, it
shows that the adsorption process has better compliance with the Langmuir adsorption
model than the Freundlich model. The Langmuir isotherm model is mostly valid for one
layer adsorption over specific number of similar surfaces. If the molecular interaction is
neglected, then it can be defined as adsorption behavior of a completely homogeneous
surface area. Despite the heterogeneity of the surface, Freundlich-type adsorption
isotherm displays the homogeneity of a Langmuir-type adsorption surface. The adsorption
of Langmuir isotherm increases linearly together with initial concentration of the adsorbate.
At maximum saturation point, the surface is coated with one layer and the amount of
adsorbate on the surface remains constant. Also, in this isotherm, the adsorption energy
is uniform. The speed of adsorption is directly proportional to the adsorbate concentration
and the active places over the surface. The speed of desorption is directly proportionate to
the amount of adsorbate adsorbed on the surface.
Thermodynamic Parameters
The thermodynamic parameters such as standard Gibbs fee energy (ΔG), entropy change
(ΔS) and enthalpy (ΔH) were calculated using following equations (17, 5):
ܭ
ௗ
=
బ
ି
×
(3)
݈݊ܭ
ௗ
=
∆ௌ
ோ
−
∆ு
ோ்
(4)
∆ܩ = ∆ܪ − ܶ∆ܵ (5)
where K
d
is the equilibrium constant, C
0
initial concentration (mg/dm
3
), C
e
equilibrium
concentration, V volume (cm
3
), m of the pumice (g), T (Kelvin), and R gas constant (8.314
J/mol). The changes in enthalpy (ΔH) and entropy (ΔS) were determined from the slope
and intercept of the plots of lnK
d
versus 1/T. The Gibbs free energy (ΔG) was calculated
using Eq (5).
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531
Table 3. Thermodynamic parameters of Neutral Red adsorption on Van Pumice.
Temp (K) K
c
ΔG, kJ/mol ΔH, kJ/mol ΔS, kJmol
-1
K
-1
298
2,6502
-
2414,6987
0,0013 0,0292
308
7,5660
-
5182,0370
318
8,4715
-
5649,1358
Concerning the adsorption of Neutral Red solutions onto the Pumice found in Lake Van,
thermodynamic parameters such as ΔG, ΔS and ΔH were determined at temperatures of
298, 308, and 318 K.
The negative value of Gibbs free energy (ΔG) shows that the adsorption process of Neutral
Red onto the Pumice located in Lake Van is spontaneous. The (ΔG) value tends to decrease
at increasing temperatures and thus demonstrates that this process can be carried out
much easier at high temperatures. The positive value of ΔS shows that, at the interface
between Neutral Red solution and the Pumice found in Lake Van, the sorption process
tends toward increasing disorder. The positive value of ΔH points out that the sorption
process is endothermic.
Adsorption Kinetics
The experimental data relating to adsorption of dye onto pumice was investigated using
the Lagergren pseudo-first and pseudo-second order equation (1, 7):
݈݃ሺܳ
− ܳ
௧
ሻ= ݈݃ሺܳ
ሻ−
భ
௧
ଶ.ଷଷ
(6)
௧
=
ଵ
మ
మ
+
ଵ
ݐ (7)
where, q
e
is the amount of dye adsorbed at equilibrium (mg/g), q
t
amount of dye adsorbed
at various times, t time of adsorption duration, and k
1
is a rate constant of the equation
(min
–1
).
The k
1
and q
e
were calculated from the slope and intercept of the plots of log (q
e
– q
t
)
versus t according to the pseudo-first-order model (Fig. 1) and t/q
t
versus t according to
the pseudo-second-order model (Fig. 2) as well as q
e
and k
2
from the slope and intercept
were calculated.
Kul, Benek, Selçuk, and Onursal, JOTCSA. 2017; 4(2): 525-536. RESEARCH ARTICLE
532
Figure 1: Pseudo first order graph of Dye Adsorption on Van Pumice.
Figure 2: Pseudo second order graph of Dye Adsorption on Van Pumice
Table 4. Pseudo first order parameters of the dye.
T (K) k
1
q
e
(calc.) q
e
(exp.) R
2
298
0,0215
2,7455
18,1510
0,7089
308
0,0374
7,8126
22,0815
0,8870
318
0,0357
3,0300
22,3605
0,7560
Table 5. Pseudo second order parameters of the dye.
T (K) k
2
q
e
(calc.) q
e
(exp.) R
2
298 0,0250 18,2929 18,1510 0,9995
308 0,0115 22,5745 22,0815 0,9987
318 0,0388 22,5004 22,3605 0,9998
Regarding all the initial pumice amounts and temperature values of pumice, we concluded
that the kinetics of sorption onto the pumice has indicated a good compliance with the
quadratic form of the kinetic model. The correlation factor R
2
was found above 0,99.
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533
CONCLUSION
Considering all these results, we have concluded that the Pumice found in Lake Van is a
recommended adsorbent for the used dyestuff. We consider that the Pumice found in Lake
Van which is currently used in many fields of application, can also be used as an adsorbent.
In his Master of science thesis, “BIOSORPTION OF VICTORIA BLUE R (VBR) ONTO
IMMOBILIZED BIOMASS OF BONE CHAR AND SUNFLOWER HUSK”, Ozdemir has applied
his experimental data to the Langmuir isotherm model and obtained the resulting R2 values
at different temperatures, varying between 0,974 and 0,989. He later found out that these
high regression coefficients and its biosorption have indicated good compliance with the
Langmuir isotherm. Compliance with Langmuir isotherm showed out that the biosorption
occured on homogenous surfaces and the dye material VMR has coated the KIKU, forming
only one layer (20).
In his master of science thesis “Removal of Dye Materials from Aqueous solutions by
Adsorption on Coals and Cokes”, Kayacan has observed that both types of cokes comply
with the Freundlich isotherm and also with the Langmuir isotherms at the same time.
Besides, the MKP cokes rather comply with the Langmuir isotherm and the DB cokes
comply with Freundlich isotherm. It is thereby concluded that the MKP cokes have relatively
homogenous surfaces, but on the other hand, the DB cokes have relatively heterogeneous
surface. He found out that the b values of Langmuir’s isotherm of MKP cokes were relatively
high, thus he concluded that this is a clear proof of why these cokes are good adsorbents
(14). It is clear that both studies support our study.
In their studies, Turkmenoglu and her friends have used acidic Pumice found in Lake Van
in sizes of 0-2 mm, 2-4 mm and 4-8 mm respectively. They have found the physical
features of Pumice found in Lake Van as follows (25):
Van Pumice
0
-
2 mm
2
-
4 mm
4
-
8 mm
Specific Weight Factor
1,72
1,32
1,06
Water Absorption Rate (%)
-
36,71
38,83
Bulk Density (kg/m
3
)
636
495
413
The chemical and physical features of Pumice are some of those determining factors to find
out if it is a good adsorbent or not.
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REFERENCES
1. Aivalioti M, Papoulias P, Kousaiti A, Gidarakos E. Adsorption of BTEX, MTBE and TAME on natural
and modified diatomite. Journal of hazardous materials. 2012;207:117–127.
2. Aksay E. Investigation of the Technological Properties of the Izmir-Menderes Pumice Ore.
[İzmir]: Dokuz Eylül University; 2005.
3. Bardakci B, Cicek E. Use of Isparta Pumice for the Removal Radioactive Waste by Adsorption. In
Isparta; 2005.
4. Başer İ, İnanıcı Y. Boyarmadde kimyası. Marmara Üniversitesi; 1990.
5. Caliskan N, Kul AR, Alkan S, Sogut EG, Alacabey I. Adsorption of Zinc (II) on diatomite and
manganese-oxide-modified diatomite: A kinetic and equilibrium study. Journal of hazardous
materials. 2011;193:27–36.
6. Cevikbas A, Ilgun F. Geology and Economics of Turkey Pumice. In: Geology and Economics of
Turkey Pumice. Isparta; 1997. p. 13–8.
7. Chen M, Shang T, Fang W, Diao G. Study on adsorption and desorption properties of the starch
grafted p-tert-butyl-calix [n] arene for butyl Rhodamine B solution. Journal of hazardous materials.
2011;185(2):914–921.
8. Çiftçi E. Yerbilimleri teknik terimler sözlüğü. (Earth Science Technical Words dictionary) NİĞDE,
Hamle Yayıncılık. 2003;580.
9. Depci T, Kul AR, Onal Y, Disli E, Alkan S, Turkmenoglu ZF. Adsorption of crystal violet from
aqueous solution on activated carbon derived from Gölbaşi lignite. Physicochemical Problems of
Mineral Processing. 2012;48(1):253–270.
10. Doğan M, Alkan M, Demirbaş Ö, Özdemir Y, Özmetin C. Adsorption kinetics of maxilon blue GRL
onto sepiolite from aqueous solutions. Chemical Engineering Journal. 2006 Nov;124(1–3):89–101.
11. Barker, J.M. and Austin, G.S. (1994): Stone, Decorative; in Carr, D.D., Senior Editor Industrial
Minerals and Rocks, Society for Mining, Metallurgy and Exploration, Littleton, Colorado, 367–378.
12. Ghosh D, Bhattacharyya KG. Adsorption of methylene blue on kaolinite. Applied Clay Science.
2002 Feb;20(6):295–300.
13. Ilhan S, Nurbas M, Ekmekci S, Ozdag H. Use of Pumice as Adsorbent in Biotechnology. In
Isparta; 1997. p. 39–46.
Kul, Benek, Selçuk, and Onursal, JOTCSA. 2017; 4(2): 525-536. RESEARCH ARTICLE
535
14. Kayacan S. Removal Of Dye Materials From Aqueous Solutions By Adsorption On Coals And
Cokes [Master’s thesis]. [Ankara]: Ankara University; 2007.
15. Khan T, Sharma T, Ali I. Adsorption of Rhodamine B dye from aqueous solution onto acid
activated mango (Magnifera indica) leaf powder: Equilibrium, kinetic and thermodynamic studies. J
Toxicol Environ Health Sci. 2011;3(10):286–97.
16. Kuscu M, Gedikoglu A. Geological Position of Regional Pumices of Isparta-Golcuk. Engineering
Geology Journal. 1990;37:69–78.
17. Laidler K, Meiser J. In: Physical Chemistry. Houghton Mifflin, New York; p. 852.
18. Mohan D, Singh KP, Singh G, Kumar K. Removal of dyes from wastewater using flyash, a low-
cost adsorbent. Ind Eng Chem Res. 2002;41(15):3688–3695.
19. Özcan Y, Ulusoy E. Tekstil Elyaf ve Boyama Tekniği. İstanbul: İstanbul Üniversitesi; 1978.
20. Özdemir N. Biosorption of Victoria Blue R (VBR) Onto Immobilized Biomass Of Bone Char And
Sunflower Husk [Master’s thesis]. [Çorum]: Hitit University; 2015.
21. Reyhanoğlu M. Pumice and its uses [Master’s thesis]. [Adana]: Çukurova University; 1988.
22. Sariisik A, Tozacan B, Davraz M, Ugur I, Cankiran O. Pumice technology. Isparta: Süleyman
Demirel University; 1998.
23. Senthilkumaar S, Kalaamani P, Subburaam C. Liquid phase adsorption of Crystal violet onto
activated carbons derived from male flowers of coconut tree. Journal of Hazardous Materials. 2006
Aug 25;136(3):800–8.
24. Tozum S. Removal of pollutants from Olive Wastewater (Karasu) with Pumicce by Adsorption
[Master’s thesis]. [Isparta]: Süleyman Demirel University; 2009.
25. Turkmenoglu Z, Kilic A, Depci T. Determination of Mechanical Properties of Self Compacting
Lightweight Concrete Manufactured with Pumice in Van Region. Çukurova Üniversitesi Mühendislik
Mimarlık Fakültesi Dergisi. 2015;30(1):105–116.
26. Yanik S. The usability of basic pumice as a concrete aggregate [Master’s thesis]. [Adana]:
Çukurova University; 2007.
Kul, Benek, Selçuk, and Onursal, JOTCSA. 2017; 4(2): 525-536. RESEARCH ARTICLE
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