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Treatment of petroleum industry wastewater using TiO2/UV photocatalytic

process

Article  in  Journal of the Indian Chemical Society · March 2015

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Feb-15-6 p6.5

J. Indian Chem. Soc.,

Vol. 92, February 2015, pp. 219-222

Treatment of petroleum industry wastewater using TiO2/UV

photocatalytic process
Niraj S. Topare*, Martin Joy, Ratnadeep R. Joshi, Pradeep B. Jadhav and Lalitkumar K. Kshirsagar
Department of Petroleum & Petrochemical Engineering, Maharashtra Institute of Technology,
Paud Road, Kothrud, Pune-411 038, Maharashtra, India
E-mail : [email protected], [email protected]
Manuscript received online 09 July 2014, revised 01 August 2014, accepted 16 August 2014

Abstract : In the present study, degradation of petroleum industry wastewater has been investigated through laboratory
experiments by employing heterogeneous photocatalytic process. A photocatalytic reactor was used for the advanced oxi-
dation. The industrial wastewater was characterized. Photocatalytic activity of semiconductor such as titanium dioxide
(TiO2 ) has been investigated. An attempt has been made to study the effect of process parameters through amount of
catalyst, and operating pH on photocatalytic degradation of petroleum industry wastewater. The experiments were car-
ried out by varying pH (2–11), amount of catalyst (0.25–1.5 g/L). Optimal suspended catalyst concentration, fluid pH
and temperature were obtained at amounts of near 1 g/L, 3 and 50 ºC, respectively. The maximum rate of degradation
was observed in acidic medium at pH 3 and maximum reduction in chemical oxygen demand (COD) of 60%.

Keywords : Wastewater, photo-catalysis, photocatalytic degradation, COD, TiO 2 .

Introduction the organic pollutants into harmless inorganic substances

Huge amounts of water are used in a petroleum refi- such as CO2 and H2O under moderate conditions. AOPs
nery and, consequently, significant volumes of wastewa- generate hydroxyl radical, a strong oxidant, which can
ter are generated. The traditional treatment of refinery completely degrade or mineralize the pollutants non-se-
wastewater is based on the physicochemical and mechanical lectively into harmless products5.
methods and further biological treatments in the integrated Titanium dioxide (TiO2) is generally considered to be
activated sludge treatment units. The contamination of the best photocatalyst and has the ability to detoxificate
water supplies by organic molecules is an increasing prob- water from a number of organic pollutants. However wide-
lem mainly because many of these molecules are not readily spread use of TiO2 is uneconomical for large-scale water
degraded by conventional methods for the treatment of treatment, thereby interest has been drawn toward the
effluents1. Besides causing visual pollution, this kind of search for suitable alternatives to TiO2 6. Many attempts
pollutant has high levels of toxicity, non-biodegradability have been made to study photocatalytic activity of diffe-
and resistance to destruction2. Several solutions are pro- rent semiconductors such as SnO 2, ZrO2, CdS and
posed in this regard, including use of coagulation en- Nb2O5 7, compared the photocatalytic activity of TiO2,
hanced by centrifugation, ultra filtration3 or sorption on SnO2, ZnS, Nb2O5 and CdS for the degradation of petro-
organ minerals4 with a level of advantage for each. These leum wastewater and found TiO2 to be the most effective
methods are not efficient and cost effective for wastewa- catalyst.
ters containing high concentration of more toxic pollut-
ants. This requires some novel techniques to transfer the Experimental
highly toxic pollutants chemically into benign species. Chemicals :
Advanced oxidation processes (AOPs) are more efficient, Titanium dioxide (99.7%) was used as a photo cata-
cheap, and ecofriendly in the degradation of any kind of lyst and purchased from Molychem, India. The wastewa-
toxic pollutants. These processes can completely degrade ter was collected from petroleum industry. Distilled wa-

219
 J. Indian Chem. Soc., Vol. 92, February 2015

ter was used for preparation of various solutions. pH of radation experiments, fixed amount of photo catalyst TiO2
the solutions was adjusted with 1 N H2SO4 or 1 N NaOH. was added to 500 mL of wastewater in each run at defi-
All others chemical used were of analytical grade. nite pH. The suspension was subjected to irradiation un-
Characterization of the wastewater : der UV light and starring with help of magnetic stirrer
for a fixed interval of time. At different time intervals, a
The petroleum industry wastewater samples were ob-
sample was taken out with the help of a pipette and then
tained, after pretreatment and before the treatment. Com-
centrifuge to remove the catalyst. The removal efficiency
position of the wastewater used in this study was ana-
(% Removal) was calculated from the following formula :
lyzed before the experimental studies. The pH values of
the effluent samples used in the experimental studies. The % Removal = [(CODi – CODf)/CODi] × 100
characteristics of petroleum industry wastewater are shown where CODi and CODf stands stand the initial and after
in Table 1. any irradiation time, COD values.
Analytical analysis :
Table 1. Characteristics of petroleum industry wastewater
The COD test was performed by Wet Chemical Oxi-
Parameter Raw effluent
pH 4.5
dation method. It is used to measure the oxygen demand
Turbidity (NTU) 450
for the oxidation of organic matters by a strong chemical
TDS (mg/L) 578 oxidant which is equivalent to the amount of organic
Conductivity (s/m) 122 matters in sample.
TSS (mg/L) 468
Results and discussion
Carbonate (mg/L) Nil
Dissolved oxygen (mg/L) 1.8 The experiments were carried out to study the degra-
Chlorine demand (mg/L) 1.9 dation wastewater employing TiO2 as catalyst under UV
COD 8200 light. Various parameters which affect the removal effi-
ciency such as catalyst loading (0.25–1.5 g/L), pH (2–
Experimental setup and procedure : 11) and were assessed under UV light.
The photo-catalytic degradation was carried out in batch Effect of catalyst concentration :
reactor as shown in Fig. 1. The light source was 400 W Fig. 2 shows the effect of catalyst loading (TiO2) on
UV lamp in the range 200–550 wavelengths. For the deg- the degradation of petroleum industry wastewater. Al-
most no pollutant elimination was achieved with UV light

Fig. 1. Experimental setup for degradation of petroleum industry Fig. 2. Effect of catalyst concentration on degradation of wastewa-
wastewater. ter.

220
 Topare et al. : Treatment of petroleum industry wastewater using TiO2/UV etc.

alone, while results show the significant degradation in as a function of pH. It has been observed that the degra-
the presence of catalyst. It can be seen that initial slopes dation efficiency initially increases with increases in pH
of the curves increase greatly by increasing catalyst load- then decrease with increases in pH, exhibiting maximum
ing (TiO2) from 0.25 to 1 g/L for petroleum industry rate of degradation at pH 3 in case of catalyst loading (1
wastewater, thereafter a decrease is appropriate after the g/L TiO2).
same irradiation times. The photo-catalytic destruction of Effect of temperature :
other organic pollutants has also exhibited the same de-
pendency on catalyst dose8. This can be explained on the The effect of temperature was tested by adjusting the
basis that optimum catalyst loading is found to be depen- temperatures petroleum industry wastewater samples at
dent on initial solute concentration because with the in- different temperatures in the range of 25–50 ºC. Fig. 4
crease in catalyst dosage, total active surface area in- shows the removal of organic compounds in the petro-
creases, hence availability of more active sites on catalyst
surface9. At the same time, due to an increase in turbidity
of the suspension with high dose of photo-catalyst, there
will be decrease in penetration of UV light and hence
photo-activated volume of suspension decreases10. Thus
it can be concluded that higher dose of catalyst may not
be useful both in view of aggregation as well as reduced
irradiation field due to light scattering. Therefore the cata-
lyst doses 1 g/L of TiO2 were fixed for further studies.
Effect of pH :
pH has important influence on pollutant molecules,
catalyst surface charge, and also on the mechanism. Waste-
water is discharged at different pH. In order to study the
effect of pH on the degradation efficiency, experiments
were carried out at various pH values, ranging from 2 to
11 for the catalyst loading 1 g/L TiO2. The pH of each of Fig. 4. Effect of temperature on degradation of wastewater at (TiO2
sample was adjusted at different value using 1 N of sulfu- dose – 1 g/L, pH 3).
ric acid or sodium hydroxide solutions. Fig. 3 shows the
degradation efficiency of petroleum industry wastewater leum industry wastewater for experiments conducted at
different temperatures. Increase of temperature from 20
to 50 ºC has reduced the required time for the pollutants
removal. The degradation is favored for most cases by
increasing temperature. The reason is related to the TiO2
electron transfers in valance bond to higher energy levels
and hence facilitating the electron hole production. The
recombination of electron hole on the surface of
photocatalysts will be also promoted by temperature en-
hancement; however, logically, this promotion will be
less extensive when density of the electron holes is high
due to high TiO2 dosage and effective irradiation. Mean-
while, temperature reduces the oxygen solubility in water
which is not desirable. On the other hand, increasing
temperature causes a global reaction improvement, ac-
cording to the Arrhenius equation, but an entropy in-
Fig. 3. Effect of pH on degradation of wastewater at (TiO2 dose crease and a less adsorption tendency into the catalyst
– 1 g/L).

JICS-8 221
 J. Indian Chem. Soc., Vol. 92, February 2015

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