Applied Surface Science 303 (2014) 14–22

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Applied Surface Science

journal homepage: www.elsevier.com/locate/apsusc

Hydrothermally modified fly ash for heavy metals and dyes removal

in advanced wastewater treatment
Maria Visa ∗ , Andreea-Maria Chelaru
Transilvania University of Brasov, Renewable Energy Systems and Recycling R&D Department, Eroilor 29, 500036 Brasov, Romania

a r t i c l e i n f o a b s t r a c t

Article history: Fly ash resulted from coal burning is a waste that can be used in wastewater treatment for removal of
Received 9 October 2013 dyes and heavy metals by adsorption.
Received in revised form 7 February 2014 Class “F” fly ash (FA), collected from the Central Heat and Power (CHP) Plant Brasov (Romania), with
Accepted 7 February 2014
oxides composition SiO2 /Al2 O3 over 2.4 was used for obtaining a new substrate with good adsorption
Available online 26 February 2014
capacity for dyes and heavy metals from wastewater. A new material was obtained from modified fly ash
with NaOH and hexadecyltrimethylammonium bromide (HTAB) a cationic surfactant. Contact time, opti-
Keywords:
mum amount of substrate and the pH corresponding to 50 mL solution of pollutants were the parameters
Fly ash
Hydrothermal synthesis
optimized for obtaining the maximum efficiency in the adsorption process. The optimized adsorption
Heavy metal parameters were further used in thermodynamic and kinetic studies of the adsorption processes.
Dye The adsorption kinetic mechanisms, and the substrate capacities are further discussed correlated with
Cationic surfactant the surface structure (XRD), composition (EDS, FTIR), and morphology (SEM, AFM).
The results indicate that the novel nano-substrate composite with fly ash modified can be used as an
efficient and low cost adsorbent for simultaneous removal of dyes and heavy metals, the resulted water
respects the discharge regulations.
© 2014 Elsevier B.V. All rights reserved.

1. Introduction
Textile industry is among the most polluting industries
regarding the fact that it uses a large amount of water during the
dyeing process [1] and because of this the discharged effluents are
loaded with numerous pollutants like dyes, toxic metals, suspended
solids, microbial pathogens and parasites, biodegradable, volatile
and recalcitrant organic compounds [2,3]. The effluents from textile
industry change the biological life of rivers and lakes [4,5].
Wastewaters with a load like this cause damages to the environ-
ment by creating problems to the groundwater resources [6]. These
wastewaters are highly colored, have a fluctuating pH, high temper-
ature and chemical oxygen demand, large amounts of suspended
oils. The main problem related to the dyes (which are stable to light
and are not biodegradable [2]) in wastewater is the color which
decreases the light permeability thus causing a negative effect on
photosynthesis [7]. Decreasing permeability of light, the amount
of oxygen decomposed lead to extinction of some living beings
and to restriction of the reuse of water. The heavy metals from the
∗ Corresponding author. Tel.: +40 729109355.
E-mail addresses: maria.visa@unitbv.ro (M. Visa), andreea.chelaru1@yahoo.com
(A.-M. Chelaru).
dyes structure represent also a problem. Metals are present in dyes
because they are used as catalysts during the manufacture of some
dyes and can be present as impurities or exist into dye molecule,
forming an integral structural element [1].
The presence of heavy metals in wastewater is unwanted due to
their solubility in water thus can be absorbed by living organisms
and like this they enter in the food chain and start to accumulate in
the human body. Ingestion of heavy metals beyond the permitted
concentration can cause serious health disorders [8].
Because of the problems caused by the presence of dyes and
heavy metals in wastewater their removal started to become
important and for this several methods like: adsorption, coagula-
tion, flocculation, precipitation, reverse osmosis, biological process,
ionizing, gamma radiations, photocatalysis are being used. But
many of these methods are expensive and when they are applied
for treating large amounts of waters, from all of them the adsorp-
tion techniques are preferred because of their advantages: low
cost, ease of operation, efficiency, simplicity of the equipment and
mostly because the adsorbent can be chosen from a wide variety of
materials, natural, synthetic and wastes, for example fly ash [9].
Fly ash is one of the most known waste and it is being used as raw
material in many industries such as cement industry, but its neg-
ative effect on the environment cannot be completely neutralized
by doing this, so reusing it as an adsorbent in removal of different

http://dx.doi.org/10.1016/j.apsusc.2014.02.025
0169-4332/© 2014 Elsevier B.V. All rights reserved.
22 M. Visa, A.-M. Chelaru / Applied Surface Science 303 (2014) 14–22
Fig. 13. Removal efficiency of HM cations and MB vs. FAA-CS24 substrate dose in
adsorption process.
Fig. 14. The methlene blue protonated by electrophilic attack.
Supplementary, after adsorption and filtration the sub-
strate loaded with pollutants was dried at 125 ◦ C and
subjected to desorption process. After 48 h, for ratio
mpFAA-CS/Cd+MB :Vbidistilled water = 0.3 g:100 mL there are no desorp-
tion of cadmium. Very small concentration of methylene blue was,
but not evaluated by spectrophotometer. These materials can be
reused for stuffing in blocks of stone.
4. Conclusions
This results show that the fly ash has potential to be used as
an alternative and cheap source of silica or alumino-silicates in the
production of adsorbents.
Micro-nano substrate was obtained in a hydrothermal process,
starting from fly ash powder and HTAB cationic surfactant and was
tested for simultaneous removal of heavy metal cations and dyes,
in a single step process by adsorption.
The FAA-CS24 structural, morphology analysis and pore distri-
bution showed that the substrate has a high crystallinity degree
and a surface with broad open pores, efficient in heavy metals (Cd2+
and/or Cu2+ ) removal from systems also containing methylene blue.
The kinetic and thermodynamic studies show that the substrate
has a good adsorption capacity mainly based on the electrostatic
attractions between the substrate and Cd2+ and/or Cu2+ cations.
Of the two substrates, FAA-CS24 substrate is effective in remov-
ing the pollutants by adsorption process and more economical in
terms of the process of obtaining, the energy consumption is lower.
Acknowledgment
This work was supported by the grant PNII-RU-TE-2012-3-
0177/2013, financed by Romanian National Authority for Scientific
Research, CNCS – UEFISCDI.
References
[1] G. Bitton, Wastewater Microbiology, John Wiley & Sons, Inc, USA, 1994, pp.
63–65.
[2] M. Sidat, H.C. Kasan, F. Bux, Laboratory-scale investigation of biological phos-
phate removal from municipal wastewater, Water SA 25 (1999) 459–462.
[3] M. Dogan, Y. Ozdemir, M. Alkan, Adsorption kinetics and mechanism of cationic
methyl violet and methylene blue dyes onto sepiolite, J. Dyes Pigments 75
(2007) 701–713.
[4] Y.S. Ho, G. McKay, The kinetic of sorption of basic dyes from aqueous solution
by sphagnum Moss peat, Can. J. Chem. Eng. 76 (1998) 822.
[5] G.M. Walker, L. Hansen, J.A. Hanna, S.J. Allen, Kinetics of a reactive dye adsorp-
tion onto dolomitic sorbents, Water Res. 37 (2003) 2081.
[6] M. Arami, N.Y. Limaee, N.M. Mahmoodi, N.S. Tabrizi, Removal of dyes from
colored textile wastewater by orange peel adsorbent: equilibrium and kinetic
studies, J. Colloid Interface Sci. 288 (2005) 371–376.
[7] V.J.P. Poots, G. Mckay, J.J. Healy, Removal of basic dye from effluent using wood
as an adsorbent, J. Water Pollut. Control Fed. 50 (1978) 926.
[8] S. Babel, T.A. Kurniawan, Cr(VI) removal from synthetic wastewater using
coconut shell charcoal and commercial activated carbon modified with oxi-
dizing agents and/or chitosan, Chemosphere 54 (2004) 951–967.
[9] P. Himanshu Patel, R.T. Vashi, Treatment of textile wastewater by adsorption
and coagulation, E-J. Chem. 7 (2010) 1468–1476.
[10] M. Visa, A. Duta, Methyl-orange and cadmium simultaneous removal using fly
ash and photo-Fenton systems, J. Hazard. Mater. 244 (2013) 773–779.
[11] B.W. Ramme, M.P. Tharaniyil, Coal Combustion Products Utilization Handbook,
2nd ed., Manufactured in the U.S. of America, 2004, pp. 15–18.
[12] M. Visa, F. Pricop, A. Duta, Sustainable treatment of wastewaters resulted in the
textile finishing industry, J. Clean Technol. Environ. Policy 13 (2011) 855–861.
[13] M. Visa, A. Duta, TiO2 /fly ash novel substrate for simultaneous removal of heavy
metals and surfactants, Chem. Eng. J. 223 (2013) 860–868.
[14] M. Šljivić, I. Smičiklas, S. Pejanović, I. Plećaš, Comparative study of Cu2+ adsorp-
tion on a zeolite, clay and a diatomite from Serbia, J. Appl. Clay Sci. 43 (2009)
33–40.
[15] M. Visa, Tailoring fly ash activated with bentonite as adsorbent for complex
wastewater treatment, J. Appl. Surf. Sci. 263 (2012) 753–762.
[16] L. Ling-Chu, M. Thirumavalavan, Y.-T. Wang, J.-F. Lee, Surface area and pore
size tailoring of mesoporous silica materials by different Hydrothermal treat-
ments and adsorption of heavy metal ions, J. Colloids Surf. A: Physicochem. Eng.
Aspects 369 (2010) 223–231.
[17] J.A. Martens, J. Jammaer, S. Bajpe, A. Aerts, Y. Lorgouilloux, C.E.A. Kirschhock,
Simple synthesis recipes of porous materials, J. Microporous Mesoporous
Mater. 140 (2011) 2–8.
[18] A. Wang, T. Kabe, Fine-tuning of pore size of MCM-41 by adjusting the initial
pH of the synthesis mixtures, Chem. Commun. 20 (1999) 2067–2068.
[19] H. Misran, R. Singh, S. Beguma, M.A. Yarmo, Processing of mesoporous silica
materials (MCM-41) from coal fly ash, J. Mater. Process. Technol. 186 (2007)
8–13.
[20] A. Khorsand Zak, W.H.A. Majid, M.E. Abrishami, R. Yousefi, R. Parvizi, Synthesis,
magnetic properties and X-ray analysis of Zn0.97 X0.03 O nanoparticles (X = Mn
Ni, and Co) using Scherer and size–strain plot methods, Solid State Sci. 14 (4)
(2012) 488–494.
[21] M. Visa, L. Isac, A. Duta, Fly ash adsorbents for multi-cation wastewater treat-
ment, Appl. Surf. Sci. 258 (2012) 6345–6352.
[22] S. Chaizasith, P. Chaizasith, C. Septhum, Removal of cadmium and nickel from
aqueous solutions by adsorption onto treated fly ash from Thailand, J. Sci.
Technol. 11 (2006) 13–19.
[23] I. Horcas, R. Fernandez, J.M. Gomez-Rodriquez, J. Colchero, J. Gomez-Herrero,
A.M. Baro, Review of Scientific Instruments, WSxM5.0 78 (2007) 013705.
[24] O. Keka, C.P. NaraYan, S. Amar Nath, Zeolita from fly ash: synthesis and char-
acterization, Bull. Mater. Sci. 27 (2004) 555–564.
[25] D.M. Manohar, B.F. Noeline, T.S. Anirudhan, Adsorption performance of Al-
pillared bentonite clay for the removal of cobalt (II) from aqueous phase, J.
Appl. Clay Sci. 31 (2006) 194–206.
[26] A. Fernández-Jiménez, A. Palomo, Mid-infrared spectroscopic studies of alkali-
activated fly ash structure, J. Microporous Mesoporous Mater. 86 (2005)
207–214.
[27] N. Takeno, Atlas of Eh-pH diagrams, Intercomparison of thermodynamic,
Databases of the National Institute of Advanced Industrial Science and Tech-
nology, 2005.
[28] J. Kielland, Effective diameters of unhydrated (first value) and hydrated (second
value) ions, J. Am. Chem. Soc. 59 (1937) 1675–1678.
[29] S. Lagergren, About the theory of so-called adsorption of soluble sub-
stances, Kungliga Svenska Vetenskapsakademiens, Handlingar 24 (4) (1898)
1–39.
[30] Y.S. Ho, G. McKay, Pseudo-second order model for sorption processes, J. Process.
Biochem. 34 (1999) 51–465.
[31] S.J. Allen, G. Mc Kay, K.Z.H. Khader, Interparticle diffusion of a basic dye during
adsorption onto sphangum peat, J. Environ. Pollut. 56 (1999) 39–50.
[32] M. Visa, L. Andronic, D. Lucaci, A. Duta, Concurrent dyes adsorption and photo-
degradation on fly ash based substrates, J. Adsorpt. 1 (2011) 101–108.
[33] S. Wang, L. Li, Z.H. Zhu, Solid-state conversion of fly ash to effective
adsorbents for Cu removal from wastewater, J. Hazard. Mater. 139 (2007)
254–259.
[34] M. Misra, K. Yang, R.K. Mehta, Application of fly ash in the agglomeration of
reactive mine tailings, J. Hazard. Mater. 51 (1996) 181–192.