Use of Perovskite-type Titanate Zirconate as Photocatalysts for Textile will be filled

in by SPEA 9
Wastewater Treatment
Bergamo E. A. 1, Ferrari-Lima A. M. 1, Aranha A. C. R. 1, Ueda A. C. 1, Verri E. A. V.i2, Marques R. G. 2, (1)
Universidade Tecnológica Federal do Paraná, Apucarana,Brasil (2) Universidade Tecnológica Federal do
Paraná,, Pato Branco, Brasil. analima@utfpr.edu.br
The combined treatment of a real textile wastewater by coupling
coagulation/flocculation and heterogeneous photocatalysis has
been investigated.
Coagulation/flocculation was performed using a tannin-based
coagulant, Tanfloc. Commercial TiO 2 and Ca(ZrxTi1-x)O3
perovskites were applied as photocatalysts. The catalysts
activities were investigated under UV-C radiation. High
reductions of chemical oxygen demand were achieved with the
combined treatment, mainly when CaTiO 3 was applied.
Chemical oxygen demand reduced from 6195 mg L-1 (untreated)
to 662 mg L-1 after coagulation/flocculation and finally to
471 mg L-1 after combined treatment.

Introduction and Wastewater [6]. Prior to photocatalysis,

Photocatalysis has several promising
applications in the environmental field like
decomposition of organic pollutants and
disinfection of water [1], water splitting [2],
photoenergy conversion [3] and self-cleaning
materials [4]. Although TiO2-based materials are
the most studied for photocatalytic applications,
ternary and other complex oxide systems have
been increasingly explored as photocatalysts.
Among the various classes of materials studied,
perovskites-based photocatalysts have unique
photophysical properties and offer distinct
advantages [5].
A perovskite-type mixed oxides have the ABO3
crystal structure where cations with large ionic
radii are coordinated to 12 oxygen atoms and
occupy the A sites. Smaller cations are coordinated
to 6 oxygen atoms and occupy the B sites. The A
sites correspond to the center of the cube whereas
the B sites to octahedral positions [5]. An example
is the calcium titanate, a common perovskite with
a band gap of 3.6 eV, whose structure is presented
on the graphical illustration.
With this background, this investigation aimed
to evaluate the Ca(ZrxTi1-x)O3 perovskites with “x”
equal to 0, 0.25, 0.5, 0.75 and 1.0 on the
photodegradation of real textile wastewater (RTW)
after coagulation/flocculation treatment.
coagulation/flocculation was performed by adding
a tannin-based coagulant, Tanfloc, at 600 mg L-1
concentration under vigorous agitation during 60 s
followed by 30 min of slow agitation.
Perovskite was synthesized using the polymeric
precursor method and characterised by
photocatalytic tests. Photocatalytic tests were
performed with 0.5 g L-1 of catalyst. Reactions
were carried out for 120 min under 60W UV-C
radiation. Prior to irradiation, the wastewater-
catalyst suspension was maintained under stirring
in the dark for 15 min in order to achieve
adsorption-desorption equilibrium.
The photocatalyst performance was evaluated by
chemical oxygen demand (COD) reduction. P25
(Evonik) has also been applied for purpose of
comparison.
The photocatalytic reactor consisted of an
isolated chamber equipped with a multiple stirrer
and a 60 W UV-C radiation source (4x15W) on top
(Fig 1.).

Methods

RTW samples were collected after neutralisation

in a textile industry and characterised following Fig. 1 Schematic diagram of the photocatalytic
the Standard Methods for Examination of Water reactor system.

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 Results Fig. 2 COD reduction after 120 min of UV-C
irradiation (60 W).
Wastewater Characterisation and Coagulation
Treatment It can be clearly seen that CaTiO 3 showed the
best photocatalytic performance for the textile
In general, as depicted in Table 1, the effluent wastewater COD reduction. It seems that the
has high turbidity and COD. Reductions on modifications of the calcium titanate by
turbidity and COD after coagulation/flocculation introducing zirconium was detrimental for the
certify the high capability of Tanfloc to remove photocatalytic activity of CaTiO 3. In this sense,
organic and colloidal matter from the effluent. more efforts are needed to characterise and
understand the structure-property relations in such
Table 1 Characterisation of RTW before and zirconium and titanium based compounds,
after coagulation/flocculation improve their photocatalytic activity and better
comprehend the obtained results.
Parameter Initial After Coagulation
pH 7.12 7.48 Conclusion
Turbidity
441 31 Ca(ZrxTi1-x)O3 perovskites has been synthesised
(NTU)
COD and its performance on photocatalysis has been
6195 662.3 evaluated on the photodegradation of a real textile
(mg L-1)
wastewater after pre-treatment by
coagulation/flocculation. The best COD reduction
It is well known that pre-treatment represents an
after photocatalysis was achieved with CaTi 1O3
important step in heterogeneous photocatalysis
(x=0), however, a further characterisation of the
systems, given that high turbidity and organic
catalysts is needed in order to understand the
matter concentration can affect the scattering of
results. Chemical oxygen demand reduced from
light into the solution. It is reported that, for
6195 mg L-1 (untreated) to 662 mg L-1 after
successful photocatalysis, COD values must be
coagulation/flocculation and finally to 471 mg L-1
lower than 800 mg L-1 [1].
after combined treatment
RTS Photodegradation

After coagulation/flocculation process, the

supernatant was separated from sludge and
submitted to photodegradation under UV-C
radiation. The reduction of COD as a function of
time for each catalyst is shown on Fig. 2.

Acknowledgements. Authors acknowledge CNPq (Process number 459057/2014-6) for the financial support.

References

[1] A.M. Ferrari-Lima, R.G. Marques, N.R.C. Fernandes-Machado, M.L. Gimenes, Catal. Today 209 (2013) 79–83.

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[2] A.A. Ismail, D.W. Bahnemann, Sol. Energy Mater. Sol. C 128 (2014) 85–101.
[3] K. Nakata, T. Ochiai, T. Murakami, A. Fujishima, Electrochim. Acta 84 (2012)103–111.
[4] Q. Li, X. Wang, X. Lu, H. Tian, H. Jiang, G. Lv, D. Guo, C. Wu, B. Chen, Biomaterials 30 (2009) 4708–4715.
[5] P. Kanhere, Z Chen, Molecules 19 (2014) 19995-20022.
[6] Standard Methods for the Examination of Water and Wastewater , APHA, Washington, 20th edition, 1998.

1. Poster
2. I apply for student SPEA9 grant to cover my accomodation costs in Strasbourg : No
3. Chosen topics by order of preference
Topic 1: Photocatalytic hybrid systems
Topic 2: Environmental photochemistry and photocatalysis
Topic 3: Novel materials for photochemistry and photocatalysis
Suggested Topic : Photocatalysis with real wastewater
4. Special Issues of SPEA 9
Contribution to Special Issues of SPEA 9 ? Yes Journal name: Environmental Science and Pollution
Research
5. Free keywords
Keywords: combined treatment, perovskites, photocatalysis, textile wastewater