Different samples
of Ce- and S-codoped TiO2 nanoparticles
were prepared through simple sol–gel synthesis method by using
cerium nitrate hexahydrate as cerium precursor, thiourea as sulfur,
and tetrabutyl titanate (TBOT) as titanium precursor. Characterization
of prepared samples were done by various techniques such as, X-ray
diffraction (XRD), UV–visible diffuse reflectance spectroscopy,
transmission electron microscopy, Fourier transformation infrared
spectroscopy, photoluminescence spectroscopy, and X-ray photoelectron
spectroscopy. The XRD showed the presence of only anatase TiO2 for the single sulfur-doped and cerium- and sulfur-codoped
titania samples. XRD analysis also pointed out the decrease in the
crystal size with the increase in Ce concentration in the samples.
The BET analysis reported an increase in the surface area and decrease
in the pore size with the increase in the Ce concentration. The PLS
results of the samples first showed a decrease in the intensity of
the spectra sync with the reduction of recombination centers when
the Ce was introduced in codoped TiO2 with the maximum
decrease for 0.04 Ce/S-codoped titania; with the further increase
in the Ce concentration in the samples, the intensity of the spectra
gradually increased coinciding with the increase in the recombination
centers. The recombination centers exhibit a direct relationship with
the photocatalytic activity of the samples, which could be evidenced
by the decolorization of 25 mg/L solution of AO-7. The activity of
codoped samples was first increased by the incorporation of Ce with
the maximum degradation for 0.04 cerium- and sulfur-codoped titania.
By the further increase in the Ce amount in the Ce- and S-codoped
titania samples the activity was shown to decrease gradually.
The alkylation kinetics of isobutane
with butene using sulfuric
acid as catalyst was investigated by batch experiments in the conditions
of industrial interest. More than 16 alkylates were identified and
quantified by GC-MS. On the basis of the classic carbonium ion mechanism,
the kinetic model was established, which can predict the concentration
change of three groups of key alkylates including trimethylpentanes
(TMPs), undesirable dimethylhexanes (DMHs), and heavy ends (HEs).
The agreement between experimental and model calculated data was quite
satisfactory. The rate constants were found to be constant with the
varied temperatures (276.2 to 285.2 K) except those accounting for
the addition of H+ to isobutene and its reversible reaction.
An anti-Arrhenius behavior was observed for the addition reaction
of H+ to isobutene, in which the corresponding rate constant
falls with the increasing temperatures. The kinetic model was confirmed
by the simulation of the industrial alkylation reactor. Hopefully,
the kinetic model developed in this work will be useful to the design
and optimization of novel alkylation reactors.
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