ISSN 1070-4272, Russian Journal of Applied Chemistry, 2016, Vol. 89, No. 12, pp. 2076−2083. © Pleiades Publishing, Ltd., 2016.
The text was submitted by the authors in English.
Photocatalytic Oxidative Desulfurization of Model Oil
Catalyzed by TiO
with Different Crystal Structure
in the Presence of Phase Transfer Catalyst
, Ningfang Zhu
, Bo Chen
, Fang Wang
, and Xueqin Wang
College of Chemistry & Chemical Engineering, Northeast Petroleum University, Daqing 163318, Heilongjiang, China
Provincial Key Laboratory of Oil & Gas Chemical Technology, Northeast Petroleum University, Daqing, 163318, China
Personnel Department, Northeast Petroleum University, Daqing 163318, Heilongjiang, China
Department of Petroleum Engineering, Northeast Petroleum University, 163318 Daqing, China
Received January 18, 2017
Abstract—The photocatalytic oxidative desulfurization is one of the promising processes to realize the deep
desulfurization of the fuel. A series of TiO
NPs) were prepared to investigate the effect of
annealing temperatures on its physical properties and the photocatalytic oxidative desulfurization performance.
Their physicochemical properties were investigated by X–ray diffraction (XRD), fourier transform infrared spec-
troscopy (FTIR), thermal gravimetric and differential thermal analysis (TG–DTA), scanning electron microscopy
(SEM), and X–ray energy dispersive spectrometer (EDS). The results show that, the crystallite structure of TiO
NPs annealed at 250–450°C was mainly composed of anatase phase. The rutile phase appeared when the anneal
temperature increased to 550°C and all of the anatase converted into rutile phase when annealed at 750°C. The
effect of crystallite structure of TiO
on its photocatalytic oxidative desulfurization performance was investigated
using benzothiophene (BT) as the model sulfur compound. The anatase phase was preferable for the photocatalytic
oxidation of BT. Phase transfer catalyst plays an important role for improving the photocatalytic desulfurization
rate. The photocatalytic oxidative reaction mechanism was also proposed in the presence of TiO
as oxidant, and the DMDAAC as phase transfer catalyst. In the heterogeneous catalytic system, the entire
reaction rate is mainly determined by the oxidation reaction and the extraction process, in which the oxidation
process could be the rate determining step.
Sulfur compounds in fuel have caused serious
problems to both the environment and human health.
The environmental regulations have been introduced in
many countries around the world to reduce the sulfur
content of diesel fuel to ultra low levels (10 ppm)
[1, 2]. The conventional desulfurization process in the
petroleum industry is hydrodesulfurization (HDS),
which requires high pressure and high temperature
reaction system [3 –6]. However, HDS process was not
so cost-efﬁ cient to oxidize aromatic thiophenes, such as
dibenzothiophene (DBT) and benzothiophene (BT) [6, 7].
Moreover, the by-products of this industrial process lead
to secondary pollution to human beings. Therefore, the
desulfurization technology needs to be improved to satisfy
the environmental and economic demands.
Over the past decades, the semiconductor used in
catalytic degradation of organic pollutants has attracted
more and more interests owing to its unique oxidizing
ability, which derives from the photo-generated electron –
hole pairs [8 –10]. Titanium dioxide (TiO
), as one of
the most widely used semiconductor materials, exhibits
high photocatalytic reactivity with non-toxic, chemical-
stabile and pollution-free properties [11–13]. Many