Abstract: Borate minerals have attracted considerable attention in the past years due to their structural chemistry and mechanical properties in several industries. Recently, increasing attention has been paid to the use of; synthetically produced magnesium borates as catalysts reinforcing material for plastics, the conversion of hydrocarbons, electro-conductive treating agent, anti-wear and anti-corrosion materials. Magnesium borates can be synthesized by several methods such as; hydrothermal and solid-state (thermal) processes. In this study the hydrothermal production method was applied at the modest temperature of 80C along with convenient crystal growth. Using MgCl2.6H2O, H3BO3, and NaOH as starting materials, 30, 60, 120, 240 minutes of reaction times were studied. After all, the crystal structure and the morphology of the products were examined by X-Ray Diffraction (XRD) and Fourier Transform Infrared Spectroscopy (FT-IR). As a result the forms of Admontite and Mcallisterite minerals were synthesized.
Abstract: The conventional production of biodiesel from crude
palm oil which contains large amounts of free fatty acids in the
presence of a homogeneous base catalyst confronts the problems of
soap formation and very low yield of biodiesel. To overcome these
problems, free fatty acids must be esterified to their esters in the
presence of an acid catalyst prior to alkaline-catalyzed
transesterification. Sulfated metal oxides are a promising group of
catalysts due to their very high acidity. In this research, aluminadoped
sulfated tin oxide (SO4
2-/Al2O3-SnO2) catalysts were prepared
and used for esterification of free fatty acids in crude palm oil in a
batch reactor. The SO4
2-/Al2O3-SnO2 catalysts were prepared from
different Al precursors. The results showed that different Al
precursors gave different activities of the SO4
2-/Al2O3-SnO2 catalysts.
The esterification of free fatty acids in crude palm oil with methanol
in the presence of SO4
2-/Al2O3-SnO2 catalysts followed first-order
kinetics.
Abstract: Carbon nanotubes (CNTs) possess unique structural,
mechanical, thermal and electronic properties, and have been
proposed to be used for applications in many fields. However, to
reach the full potential of the CNTs, many problems still need to be
solved, including the development of an easy and effective
purification procedure, since synthesized CNTs contain impurities,
such as amorphous carbon, carbon nanoparticles and metal particles.
Different purification methods yield different CNT characteristics
and may be suitable for the production of different types of CNTs. In
this study, the effect of different purification chemicals on carbon
nanotube quality was investigated. CNTs were firstly synthesized by
chemical vapor deposition (CVD) of acetylene (C2H2) on a
magnesium oxide (MgO) powder impregnated with an iron nitrate
(Fe(NO3)3·9H2O) solution. The synthesis parameters were selected
as: the synthesis temperature of 800°C, the iron content in the
precursor of 5% and the synthesis time of 30 min. The liquid phase
oxidation method was applied for the purification of the synthesized
CNT materials. Three different acid chemicals (HNO3, H2SO4, and
HCl) were used in the removal of the metal catalysts from the
synthesized CNT material to investigate the possible effects of each
acid solution to the purification step. Purification experiments were
carried out at two different temperatures (75 and 120 °C), two
different acid concentrations (3 and 6 M) and for three different time
intervals (6, 8 and 15 h). A 30% H2O2 : 3M HCl (1:1 v%) solution
was also used in the purification step to remove both the metal
catalysts and the amorphous carbon. The purifications using this
solution were performed at the temperature of 75°C for 8 hours.
Purification efficiencies at different conditions were evaluated by
thermogravimetric analysis. Thermal and electrical properties of
CNTs were also determined. It was found that the obtained electrical
conductivity values for the carbon nanotubes were typical for organic
semiconductor materials and thermal stabilities were changed
depending on the purification chemicals.
Abstract: Copolymerization of ethylene with 1-hexene was
carried out using two ansa-fluorenyl titanium derivative complexes.
The substituent effect on the catalytic activity, monomer reactivity
ratio and polymer property was investigated. It was found that the
presence of t-Bu groups on fluorenyl ring exhibited remarkable
catalytic activity and produced polymer with high molecular weight.
However, these catalysts produce polymer with narrow molecular
weight distribution, indicating the characteristic of single-site
metallocene catalyst. Based on 13C NMR, we can observe that
monomer reactivity ratio was affected by catalyst structure. The rH
values of complex 2 were lower than that of complex 1 which might
be result from the higher steric hindrance leading to a reduction of 1-
hexene insertion step.
Abstract: The adsorption properties of CO and H2 on iron-based
catalyst with addition of Zr and Ni were investigated using
temperature programmed desorption process. It was found that on the
carburized iron-based catalysts, molecular state and dissociative state
CO existed together. The addition of Zr was preferential for the
molecular state adsorption of CO on iron-based catalyst and the
presence of Ni was beneficial to the dissociative adsorption of CO. On
H2 reduced catalysts, hydrogen mainly adsorbs on the surface iron
sites and surface oxide sites. On CO reduced catalysts, hydrogen
probably existed as the most stable CH and OH species. The addition
of Zr was not benefit to the dissociative adsorption of hydrogen on
iron-based catalyst and the presence of Ni was preferential for the
dissociative adsorption of hydrogen.
Abstract: Recently, a growing interest has emerged on the
development of new and efficient energy sources, due to the inevitable extinction of the nonrenewable energy reserves. One of
these alternative sources which has a great potential and sustainability to meet up the energy demand is biomass energy. This
significant energy source can be utilized with various energy
conversion technologies, one of which is biomass gasification in
supercritical water.
Water, being the most important solvent in nature, has very important characteristics as a reaction solvent under supercritical
circumstances. At temperatures above its critical point (374.8oC and
22.1 MPa), water becomes more acidic and its diffusivity increases.
Working with water at high temperatures increases the thermal
reaction rate, which in consequence leads to a better dissolving of the
organic matters and a fast reaction with oxygen. Hence, supercritical water offers a control mechanism depending on solubility, excellent
transport properties based on its high diffusion ability and new reaction possibilities for hydrolysis or oxidation.
In this study the gasification of a real biomass, namely olive mill
wastewater (OMW), in supercritical water is investigated with the
use of Pt/Al2O3 and Ni/Al2O3 catalysts. OMW is a by-product
obtained during olive oil production, which has a complex nature
characterized by a high content of organic compounds and
polyphenols. These properties impose OMW a significant pollution
potential, but at the same time, the high content of organics makes
OMW a desirable biomass candidate for energy production.
All of the catalytic gasification experiments were made with five
different reaction temperatures (400, 450, 500, 550 and 600°C),
under a constant pressure of 25 MPa. For the experiments conducted
with Ni/Al2O3 catalyst, the effect of five reaction times (30, 60, 90,
120 and 150 s) was investigated. However, procuring that similar
gasification efficiencies could be obtained at shorter times, the experiments were made by using different reaction times (10, 15, 20,
25 and 30 s) for the case of Pt/Al2O3 catalyst. Through these experiments, the effects of temperature, time and catalyst type on the
gasification yields and treatment efficiencies were investigated.
Abstract: Hydrodesulfurization (HDS) of dibenzothiophene
(DBT) in a high pressure batch reactor was done at 320 °C on
CoMoS/Al2O3-B2O3 (4, 10, and 16 wt. % of Boria) using nhexadecane
as solvent, dimethyldisulfide (DMDS) in tetradecane as
sulfur agent, and stirring at 1000 rpm. The effects of boria were
investigated by using X-ray diffraction (XRD), Temperature
programmed desorption (TPD) of ammonia, and Brunauer-Emmet-
Teller (BET) experiments. The results showed that the catalyst
prepared with low boria content (4 wt. %) had HDS activity (in
pseudo first order kinetic constant basis) value ~1.45 times higher to
that of CoMoS/Al2O3 catalyst.
Abstract: The elimination of ranitidine (a pharmaceutical
compound) has been carried out in the presence of UV-C radiation.
After some preliminary experiments, it has been experienced the no
influence of the gas nature (air or oxygen) bubbled in photolytic
experiments. From simple photolysis experiments the quantum yield
of this compound has been determined. Two photolytic
approximation has been used, the linear source emission in parallel
planes and the point source emission in spherical planes. The
quantum yield obtained was in the proximity of 0.05 mol Einstein-1
regardless of the method used. Addition of free radical promoters
(hydrogen peroxide) increases the ranitidine removal rate while the
use of photocatalysts (TiO2) negatively affects the process.
Abstract: In this study, production possibilities of hydrogen and/or methane via SCWG from black grape residues have been investigated. For this aim, grape residues which remain as a byproduct of the wine making process have been used. Since utilization from grape residues is limited due to the high moisture content, supercritical water gasification is the most convenient method. The effect of the gasification temperature and type of catalyst on supercritical water gasification have been investigated. Gasification experiments were performed in a batch autoclave at four different temperatures 300, 400, 500 and 600°C. K2CO3 and Trona (NaHCO3.Na2CO3·2H2O) were used as catalyst. Real biomass types of black grape residues have been successfully gasified and the product gas (hydrogen, methane, carbon dioxide, carbon monoxide and a small amount of ethane and ethylene) were identified by using gas chromatography. A TOC analyzer was used to determine total organic carbon (TOC) content of aqueous phase. The amounts of carboxylic acids, aldehydes, ketones, furfurals and phenols present in the aqueous solutions were analyzed by high performance liquid chromatography. When the temperature increased from 300°C to 600°C, mol% of H2 in gas products increased. The presence of catalysts improves the hydrogen yield. Trona showed gasification activity to be similar to that of K2CO3. It may be concluded that the use of Trona instead of commercially produced catalysts, can be preferably used in the gasification of biomass in supercritical water.
Abstract: ZnO heteronanostructured nanowires arrays have
been fabricated by low temperature solution method. Various
heterostructures were synthesized including CdS/ZnO,
CdSe/CdS/ZnO nanowires and Co3O4/ZnO, ZnO/SiC
nanowires. These multifunctional heterostructure nanowires
showed important applications in photocatalysts, sensors,
wettability control and solar energy conversion.
Abstract: Solution for the complete removal of carbon
monoxide from the exhaust gases still poses a challenge to the
researchers and this problem is still under development. Modeling for
reduction of carbon monoxide is carried out using heterogeneous
reaction using low cost non-noble metal based catalysts for the
purpose of controlling emissions released to the atmosphere. A
simple one-dimensional model was developed for the monolith using
hopcalite catalyst. The converter is assumed to be an adiabatic
monolith operating under warm-up conditions. The effect of inlet gas
temperatures and catalyst loading on carbon monoxide reduction
during cold start period in the converter is analysed.
Abstract: Palladium-catalyzed hydrodechlorination is a
promising alternative for the treatment of environmentally relevant
water bodies, such as groundwater, contaminated with chlorinated
organic compounds (COCs). In the aqueous phase
hydrodechlorination of COCs, Pd-based catalysts were found to have
a very high catalytic activity. However, the full utilization of the
catalyst-s potential is impeded by the sensitivity of the catalyst to
poisoning and deactivation induced by reduced sulfur compounds
(e.g. sulfides). Several regenerants have been tested before to recover
the performance of sulfide-fouled Pd catalyst. But these only
delivered partial success with respect to re-establishment of the
catalyst activity. In this study, the deactivation behaviour of
Pd/Al2O3 in the presence of sulfide was investigated. Subsequent to
total deactivation the catalyst was regenerated in the aqueous phase
using potassium permanganate. Under neutral pH condition,
oxidative regeneration with permanganate delivered a slow recovery
of catalyst activity. However, changing the pH of the bulk solution to
acidic resulted in the complete recovery of catalyst activity within a
regeneration time of about half an hour. These findings suggest the
superiority of permanganate as regenerant in re-activating Pd/Al2O3
by oxidizing Pd-bound sulfide.
Abstract: Three alumina-supported Pt-Sn catalysts have been
prepared by means of co-impregnation and characterized by XRD and
N2 adsorption. The influence of catalyst composition and reaction
conditions on the conversion and selectivity were investigated in the
hydrogenation of acetic acid in an isothermal integral fixed bed
reactor. The experiments were performed on the temperature interval
468-548 K, liquid hourly space velocity (LHSV) of 0.3-0.7h-1,
pressures between 1.0 and 5.0Mpa. A good compromise of
0.75%Pt-1.5%Sn can act as an optimized acetic acid hydrogenation
catalyst, and the conversion and selectivity can be tuned through the
variation of reaction conditions.
Abstract: In this study, the ability of Aspergillus niger and
Penicillium simplicissimum to extract heavy metals from a spent
refinery catalyst was investigated. For the first step, a spent
processing catalyst from one of the oil refineries in Iran was
physically and chemically characterized. Aspergillus niger and
Penicillium simplicissimum were used to mobilize Al/Co/Mo/Ni from
hazardous spent catalysts. The fungi were adapted to the mixture of
metals at 100-800 mg L-1 with increments in concentration of 100 mg
L-1. Bioleaching experiments were carried out in batch cultures. To
investigate the production of organic acids in sucrose medium,
analyses of the culture medium by HPLC were performed at specific
time intervals after inoculation. The results obtained from Inductive
coupled plasma-optical emission spectrometry (ICP-OES) showed
that after the one-step bioleaching process using Aspergillus niger,
maximum removal efficiencies of 27%, 66%, 62% and 38% were
achieved for Al, Co, Mo and Ni, respectively. However, the highest
removal efficiencies using Penicillium simplicissimum were of 32%,
67%, 65% and 38% for Al, Co, Mo and Ni, respectively
Abstract: Earlier studies in kinship networks have primarily
focused on observing the social relationships existing between family
relatives. In this study, we pre-identified hubs in the network to
investigate if they could play a catalyst role in the transfer of physical
information. We conducted a case study of a ceremony performed in
one of the families of a small Hindu community – the Uttar Rarhi
Kayasthas. Individuals (n = 168) who resided in 11 geographically
dispersed regions were contacted through our hub-based
representation. We found that using this representation, over 98% of
the individuals were successfully contacted within the stipulated
period. The network also demonstrated a small-world property, with
an average geodesic distance of 3.56.
Abstract: Hydrogen is an important chemical in many industries
and it is expected to become one of the major fuels for energy
generation in the future. Unfortunately, hydrogen does not exist in its
elemental form in nature and therefore has to be produced from
hydrocarbons, hydrogen-containing compounds or water.
Above its critical point (374.8oC and 22.1MPa), water has lower
density and viscosity, and a higher heat capacity than those of
ambient water. Mass transfer in supercritical water (SCW) is
enhanced due to its increased diffusivity and transport ability. The
reduced dielectric constant makes supercritical water a better solvent
for organic compounds and gases. Hence, due to the aforementioned
desirable properties, there is a growing interest toward studies
regarding the gasification of organic matter containing biomass or
model biomass solutions in supercritical water.
In this study, hydrogen and biofuel production by the catalytic
gasification of 2-Propanol in supercritical conditions of water was
investigated. Pt/Al2O3and Ni/Al2O3were the catalysts used in the
gasification reactions. All of the experiments were performed under a
constant pressure of 25MPa. The effects of five reaction temperatures
(400, 450, 500, 550 and 600°C) and five reaction times (10, 15, 20,
25 and 30 s) on the gasification yield and flammable component
content were investigated.
Abstract: In the present work, we have developed a symmetric electrochemical capacitor based on the nanostructured iron oxide (Fe3O4)-activated carbon (AC) nanocomposite materials. The physical properties of the nanocomposites were characterized by Scanning Electron Microscopy (SEM) and Brunauer-Emmett-Teller (BET) analysis. The electrochemical performances of the composite electrode in 1.0 M Na2SO3 and 1.0 M Na2SO4 aqueous solutions were evaluated using cyclic voltammetry (CV) and electrochemical impedance spectroscopy (EIS). The composite electrode with 4 wt% of iron oxide nanomaterials exhibits the highest capacitance of 86 F/g. The experimental results clearly indicate that the incorporation of iron oxide nanomaterials at low concentration to the composite can improve the capacitive performance, mainly attributed to the contribution of the pseudocapacitance charge storage mechanism and the enhancement on the effective surface area of the electrode. Nevertheless, there is an optimum threshold on the amount of iron oxide that needs to be incorporated into the composite system. When this optimum threshold is exceeded, the capacitive performance of the electrode starts to deteriorate, as a result of the undesired particle aggregation, which is clearly indicated in the SEM analysis. The electrochemical performance of the composite electrode is found to be superior when Na2SO3 is used as the electrolyte, if compared to the Na2SO4 solution. It is believed that Fe3O4 nanoparticles can provide favourable surface adsorption sites for sulphite (SO3 2-) anions which act as catalysts for subsequent redox and intercalation reactions.
Abstract: An efficient and green protocol for the synthesis of α-
aminonitriles derivatives by one-pot reaction of different aldehydes
with amines and trimethylsilyl cyanides has been developed using
natural alumina, alumina sulfuric acid (ASA), nano-γ-alumina, nanoalumina
sulfuric acid (nano-ASA) under microwave irradiation and
solvent-free conditions. The advantages of methods are short reaction
times, high yields, milder conditions and easy work up. The catalysts
can be recovered for the subsequent reactions and reused without any
appreciable loss of efficiency.
Abstract: The aim of this study was to synthesize the single
walled carbon nanotubes (SWCNTs) and determine their hydrogen
storage capacities. SWCNTs were firstly synthesized by chemical
vapor deposition (CVD) of acetylene (C2H2) on a magnesium oxide
(MgO) powder impregnated with an iron nitrate (Fe(NO3)3·9H2O)
solution. The synthesis parameters were selected as: the synthesis
temperature of 800°C, the iron content in the precursor of 5% and the
synthesis time of 30 min. Purification process of SWCNTs was
fulfilled by microwave digestion at three different temperatures (120,
150 and 200 °C), three different acid concentrations (0.5, 1 and 1.5
M) and for three different time intervals (15, 30 and 60 min). Nitric
acid (HNO3) was used in the removal of the metal catalysts. The
hydrogen storage capacities of the purified materials were measured
using volumetric method at the liquid nitrogen temperature and gas
pressure up to 100 bar. The effects of the purification conditions such
as temperature, time and acid concentration on hydrogen adsorption
were investigated.
Abstract: The rate of production of main products of the Fischer-Tropsch reactions over Fe/HZSM5 bifunctional catalyst in a fixed bed reactor is investigated at a broad range of temperature, pressure, space velocity, H2/CO feed molar ratio and CO2, CH4 and water flow rates. Model discrimination and parameter estimation were performed according to the integral method of kinetic analysis. Due to lack of mechanism development for Fisher – Tropsch Synthesis on bifunctional catalysts, 26 different models were tested and the best model is selected. Comprehensive one and two dimensional heterogeneous reactor models are developed to simulate the performance of fixed-bed Fischer – Tropsch reactors. To reduce computational time for optimization purposes, an Artificial Feed Forward Neural Network (AFFNN) has been used to describe intra particle mass and heat transfer diffusion in the catalyst pellet. It is seen that products' reaction rates have direct relation with H2 partial pressure and reverse relation with CO partial pressure. The results show that the hybrid model has good agreement with rigorous mechanistic model, favoring that the hybrid model is about 25-30 times faster.