Abstract: Sol-gel immobilization of enzymes, which can improve considerably their properties, is now one of the most used techniques. By deposition of the entrapped lipase on a solid support, a new and improved biocatalyst was obtained, which can be used with excellent results in acylation reactions. In this paper, lipase B from Candida antarctica was double immobilized on different adsorbents. These biocatalysts were employed in the kinetic resolution of several aliphatic secondary alcohols in organic medium. High total recovery yields of enzymatic activity, up to 560%, were obtained. For all the studied alcohols the enantiomeric ratios E were over 200. The influence of the reaction medium was studied for the kinetic resolution of 2-pentanol.
Abstract: The supported Pd catalysts were analyzed by X-ray
diffraction and X-ray absorption spectroscopy in order to determine
their global and local structure. The average particle size of the
supported Pd catalysts was determined by X-ray diffraction method.
One of the main purposes of the present contribution is to focus on
understanding the specific role of the Pd particle size determined by
X-ray diffraction and that of the support oxide. Based on X-ray
absorption fine structure spectroscopy analysis we consider that the
whole local structure of the investigated samples are distorted
concerning the atomic number but the distances between atoms are
almost the same as for standard Pd sample. Due to the strong
modifications of the Pd cluster local structure, the metal-support
interface may influence the electronic properties of metal clusters
and thus their reactivity for absorption of the reactant molecules.
Abstract: High purity hydrogen and the valuable by-product of carbon nanotubes (CNTs) can be produced by the methane catalytic decomposition. The methane conversion and the performance of CNTs were determined by the choices of catalysts and the condition of decomposition reaction. In this paper, Ni/MgO and Ni/O-D (oxidized diamond) catalysts were prepared by wetness impregnation method. The effects of reaction temperature and space velocity of methane on the methane conversion were investigated in a fixed-bed. The surface area, structure and micrography were characterized with BET, XPS, SEM, EDS technology. The results showed that the conversion of methane was above 8% within 150 min (T=500) for 33Ni/O-D catalyst and higher than 25% within 120 min (T=650) for 41Ni/MgO catalyst. The initial conversion increased with the increasing temperature of the decomposition reaction, but their catalytic activities decreased rapidly while at too higher temperature. To decrease the space velocity of methane was propitious to promote the methane conversion, but not favor of the hydrogen yields. The appearance of carbon resulted from the methane decomposition lied on the support type and the condition of catalytic reaction. It presented as fiber shape on the surface of Ni/O-D at the relatively lower temperature such as 500 and 550, but as grain shape stacked on and overlayed on the surface of the metal nickel while at 650. The carbon fiber can form on the Ni/MgO surface at 650 and the diameter of the carbon fiber increased with the decreasing space velocity.
Abstract: In this study, oxidative steam reforming of methanol (OSRM) over a Au/CeO2–Fe2O3 catalyst prepared by a depositionprecipitation (DP) method was studied to produce hydrogen in order to feed a Proton Exchange Membrane Fuel Cell (PEMFC). The support (CeO2, Fe2O3, and CeO2–Fe2O3) were prepared by precipitation and co-precipitation methods. The impact of the support composition on the catalytic performance was studied by varying the Ce/(Ce+Fe) atomic ratio, it was found that the 1%Au/CF(0.25) calcined at 300 °C exhibited the highest catalytic activity in the whole temperature studied. In addition, the effect of Au content was investigated and 3%Au/CF(0.25) exhibited the highest activity under the optimum condition in the temperature range of 200 °C to 400 °C. The catalysts were characterized by various techniques: XRD, TPR, XRF, and UV-vis.
Abstract: In this study, the transesterification of palm oil with methanol for biodiesel production was studied by using CaO–ZnO as a heterogeneous base catalyst prepared by incipient-wetness impregnation (IWI) and co-precipitation (CP) methods. The reaction parameters considered were molar ratio of methanol to oil, amount of catalyst, reaction temperature, and reaction time. The optimum conditions–15:1 molar ratio of methanol to oil, a catalyst amount of 6 wt%, reaction temperature of 60 °C, and reaction time of 8 h–were observed. The effects of Ca loading, calcination temperature, and catalyst preparation on the catalytic performance were studied. The fresh and spent catalysts were characterized by several techniques, including XRD, TPR, and XRF.
Abstract: The removal of hydrogen sulphide is required for reasons of health, odour problems, safety and corrosivity problems. The means of removing hydrogen sulphide mainly depend on its concentration and kind of medium to be purified. The paper deals with a method of hydrogen sulphide removal from the air by its catalytic oxidation to elemental sulphur with the use of Fe-EDTA complex. The possibility of obtaining fibrous filtering materials able to remove small concentrations of H2S from the air were described. The base of these materials is fibrous ion exchanger with Fe(III)- EDTA complex immobilized on their functional groups. The complex of trivalent iron converts hydrogen sulphide to elemental sulphur. Bivalent iron formed in the reaction is oxidized by the atmospheric oxygen, so complex of trivalent iron is continuously regenerated and the overall process can be accounted as pseudocatalytic. In the present paper properties of several fibrous catalysts based on ion exchangers with different chemical nature (weak acid,weak base and strong base) were described. It was shown that the main parameters affecting the process of catalytic oxidation are:concentration of hydrogen sulphide in the air, relative humidity of the purified air, the process time and the content of Fe-EDTA complex in the fibres. The data presented show that the filtering layers with anion exchange package are much more active in the catalytic processes of hydrogen sulphide removal than cation exchanger and inert materials. In the addition to the nature of the fibres relative air humidity is a critical factor determining efficiency of the material in the air purification from H2S. It was proved that the most promising carrier of the Fe-EDTA catalyst for hydrogen sulphide oxidation are Fiban A-6 and Fiban AK-22 fibres.
Abstract: In this research, CaO-ZnO catalysts (with various
Ca:Zn atomic ratios of 1:5, 1:3, 1:1, and 3:1) prepared by incipientwetness
impregnation (IWI) and co-precipitation (CP) methods were
used as a catalyst in the transesterification of palm oil with methanol
for biodiesel production. The catalysts were characterized by several
techniques, including BET method, CO2-TPD, and Hemmett
Indicator. The effects of precursor concentration, and calcination
temperature on the catalytic performance were studied under reaction
conditions of a 15:1 methanol to oil molar ratio, 6 wt% catalyst,
reaction temperature of 60°C, and reaction time of 8 h. At Ca:Zn
atomic ratio of 1:3 gave the highest FAME value owing to a basic
properties and surface area of the prepared catalyst.
Abstract: Two novel hydrodesulfurization (HDS) catalysts:
FeN4/C and FeN2/C, were prepared using an impregnation-pyrolysis
method. The two materials were investigated as catalysts for
hydrodesulfurization (HDS) and hydrodearomitization (HDA) of
model compounds. The turnover frequency of the two FeN catalysts
is comparable to (FeN4/C) or even higher (FeN2/C) than that of
MoNi/Al2O3. The FeN4/C catalyst also exhibited catalytic activity
toward HDA.
Abstract: The Ni/α-Al2O3 catalysts with different amounts of La
as promoter from 0 to 4 wt % were prepared, characterized and their
catalytic activity was investigated in syngas methanation reaction.
Effects of reaction temperature and lanthanum loading on carbon
oxides conversion and methane selectivity were also studied. Adding
certain amount of lanthanum to 10Ni /α-Al2O3 catalysts can decrease
the average NiO crystallite diameter which leads to higher activity and
stability while excessive addition would cause deactivation quickly.
Stability on stream towards deactivation was observed up to 800 min
at 500 °C, 0.1MPa and 600000 mL·g-1·h-1.
Abstract: A study concerning the photocatalytic decolourization
of Congo red (CR) dye, over artificial UV irradiation is presented.
Photocatalysts based on a commercial titanium dioxide (TiO2)
modified with transition metals (Ni, Cu and Zn) were used. The
dopage method used was wet impregnation. A TiO2 sample without
salt was subjected to the same hydrothermal treatment to be used as
reference. Congo red solutions to several pH conditions (natural and
basic) were used to evaluate photocatalytic performance of each
doped catalysts. Photodecolourization percentage was measured
spectrofotrometically after 3 h of treatment to 499 nm as response
variable. Kinetics investigations of photodegradation indicated that
reactions obey to Langmuir-Hinshelwood model and pseudo–first
order law. The rate constant studies of photocatalytic decolourization
reactions for Zn–TiO2 and Cu–TiO2 photocatalysts indicated that in
all cases the rate constant of the reaction was higher than that of TiO2
undoped. These results show that nature of the metal modifying the
TiO2 influence on the efficiency of the photocatalyst evaluated in
process. Ni does not present an additional effect compared with TiO2,
while Zn enhances the photoactivity due to its electronic properties.
Abstract: Fischer-Tropsch synthesis is one of the most
important catalytic reactions that convert the synthetic gas to light
and heavy hydrocarbons. One of the main issues is selecting the type
of reactor. The slurry bubble reactor is suitable choice for Fischer-
Tropsch synthesis because of its good qualification to transfer heat
and mass, high durability of catalyst, low cost maintenance and
repair. The more common catalysts for Fischer-Tropsch synthesis are
Iron-based and Cobalt-based catalysts, the advantage of these
catalysts on each other depends on which type of hydrocarbons we
desire to produce. In this study, Fischer-Tropsch synthesis is modeled
with Iron and Cobalt catalysts in a slurry bubble reactor considering
mass and momentum balance and the hydrodynamic relations effect
on the reactor behavior. Profiles of reactant conversion and reactant
concentration in gas and liquid phases were determined as the
functions of residence time in the reactor. The effects of temperature,
pressure, liquid velocity, reactor diameter, catalyst diameter, gasliquid
and liquid-solid mass transfer coefficients and kinetic
coefficients on the reactant conversion have been studied. With 5%
increase of liquid velocity (with Iron catalyst), H2 conversions
increase about 6% and CO conversion increase about 4%, With 8%
increase of liquid velocity (with Cobalt catalyst), H2 conversions
increase about 26% and CO conversion increase about 4%. With
20% increase of gas-liquid mass transfer coefficient (with Iron
catalyst), H2 conversions increase about 12% and CO conversion
increase about 10% and with Cobalt catalyst H2 conversions increase
about 10% and CO conversion increase about 6%. Results show that
the process is sensitive to gas-liquid mass transfer coefficient and
optimum condition operation occurs in maximum possible liquid
velocity. This velocity must be more than minimum fluidization
velocity and less than terminal velocity in such a way that avoid
catalysts particles from leaving the fluidized bed.
Abstract: Carbon nanotubes (CNTs) with their high mechanical,
electrical, thermal and chemical properties are regarded as promising
materials for many different potential applications. Having unique
properties they can be used in a wide range of fields such as
electronic devices, electrodes, drug delivery systems, hydrogen
storage, textile etc. Catalytic chemical vapor deposition (CCVD) is a
common method for CNT production especially for mass production.
Catalysts impregnated on a suitable substrate are important for
production with chemical vapor deposition (CVD) method. Iron
catalyst and MgO substrate is one of most common catalyst-substrate
combination used for CNT. In this study, CNTs were produced by
CCVD of acetylene (C2H2) on magnesium oxide (MgO) powder
substrate impregnated by iron nitrate (Fe(NO3)3•9H2O) solution. The
CNT synthesis conditions were as follows: at synthesis temperatures
of 500 and 800°C multiwall and single wall CNTs were produced
respectively. Iron (Fe) catalysts were prepared by with Fe:MgO ratio
of 1:100, 5:100 and 10:100. The duration of syntheses were 30 and
60 minutes for all temperatures and catalyst percentages. The
synthesized materials were characterized by thermal gravimetric
analysis (TGA), transmission electron microscopy (TEM) and Raman
spectroscopy.
Abstract: carbonylation of methanol in homogenous phase is
one of the major routesfor production of acetic acid. Amongst group
VIII metal catalysts used in this process iridium has displayed the
best capabilities. To investigate effect of operating parameters like:
temperature, pressure, methyl iodide, methyl acetate, iridium,
ruthenium, and water concentrations on the reaction rate,
experimental design for this system based upon central composite
design (CCD) was utilized. Statistical rate equation developed by this
method contained individual, interactions and curvature effects of
parameters on the reaction rate. The model with p-value less than
0.0001 and R2 values greater than 0.9; confirmeda satisfactory fitness
of the experimental and theoretical studies. In other words, the
developed model and experimental data obtained passed all
diagnostic tests establishing this model as a statistically significant.
Abstract: Intermetallic Ni3Al – based alloys belong to a group
of advanced materials characterized by good chemical and physical
properties (such as structural stability, corrosion resistance) which
offer advenced technological applications. The paper presents the
study of catalytic properties of Ni3Al foils (thickness approximately
50 &m) in the methanol and hexane decomposition. The egzamined
material posses microcrystalline structure without any additional
catalysts on the surface. The better catalytic activity of Ni3Al foils
with respect to quartz plates in both methanol and hexane
decomposition was confirmed. On thin Ni3Al foils the methanol
conversion reaches approximately 100% above 480 oC while the
hexane conversion reaches approximately 100% (98,5%) at 500 oC.
Deposit formed during the methanol decomposition is built up of
carbon nanofibers decorated with metal-like nanoparticles.
Abstract: Nanophotocatalysts such as titanium (TiO2), zinc (ZnO), and iron (Fe2O3) oxides can be used in organic pollutants oxidation, and in many other applications. But among the challenges for technological application (scale-up) of the nanotechnology scientific developments two aspects are still little explored: research on environmental risk of the nanomaterials preparation methods, and the study of nanomaterials properties and/or performance variability. The environmental analysis was performed for six different methods of ZnO nanoparticles synthesis, and showed that it is possible to identify the more environmentally compatible process even at laboratory scale research. The obtained ZnO nanoparticles were tested as photocatalysts, and increased the degradation rate of the Rhodamine B dye up to 30 times.
Abstract: The nickel and gold nanoclusters as supported
catalysts were analyzed by XAS, XRD and XPS in order to
determine their local, global and electronic structure. The present
study has pointed out a strong deformation of the local structure of
the metal, due to its interaction with oxide supports. The average
particle size, the mean squares of the microstrain, the particle size
distribution and microstrain functions of the supported Ni and Au
catalysts were determined by XRD method using Generalized Fermi
Function for the X-ray line profiles approximation. Based on EXAFS
analysis we consider that the local structure of the investigated
systems is strongly distorted concerning the atomic number pairs.
Metal-support interaction is confirmed by the shape changes of the
probability densities of electron transitions: Ni K edge (1s →
continuum and 2p), Au LIII-edge (2p3/2 → continuum, 6s, 6d5/2 and
6d3/2). XPS investigations confirm the metal-support interaction at
their interface.
Abstract: The nature of adsorbed species on catalytic surface
over an industrial precipitated iron-based high temperature catalyst
during FTS was investigated by in-situ DRIFTS and chemical
trapping. The formulation of the mechanism of oxygenates formation
and key intermediates were also discussed. Numerous oxygenated
precursors and crucial intermediates were found by in-situ DRIFTS,
such as surface acetate, acetyl and methoxide. The results showed that
adsorbed molecules on surface such as methanol or acetaldehyde
could react with basic sites such as lattice oxygen or free surface
hydroxyls. Adsorbed molecules also had reactivity of oxidizing.
Moreover, acetyl as a key intermediate for oxygenates was observed
by investigation of CH3OH + CO and CH3I + CO + H2. Based on the
nature of surface properties, the mechanism of oxygenates formation
on precipitated iron-based high temperature catalyst was discussed.
Abstract: The paper relates to a catalyst, comprising copperchromium
spinel, coated on carrier γ-Al2O3. The effect of preparation
conditions on the active component composition and activity
behavior of the catalysts is discussed. It was found that the activity of
carbon monoxide, DME, formaldehyde and methanol oxidation
reaches a maximum at an active component content of 20 – 30 wt. %.
Temperature calcination at 500oC seems to be optimal for the γ–
alumina supported CuO-Cr2O3 catalysts for CO, DME, formaldehyde
and methanol oxidation. A three months industrial experiment was
carried out to elucidate the changes in the catalyst composition
during industrial exploitation of the catalyst and the main reasons for
catalyst deactivation.
It was concluded that the CuO–Cr2O3/γ–alumina supported
catalysts have enhanced activity toward CO, DME, formaldehyde
and methanol oxidation and that these catalysts are suitable for
industrial application. The main reason for catalyst deactivation
seems to be the deposition of iron and molybdenum, coming from the
main reactor, on the active component surface.
Abstract: The recovery of metal values and safe disposal of
spent catalyst is gaining interest due to both its hazardous nature and
increased regulation associated with disposal methods. Prior to the
recovery of the valuable metals, removal of entrained deposits limit
the diffusion of lixiviate resulting in low recovery of metals must be
taken into consideration. Therefore, petroleum refinery spent catalyst
was subjected to acetone washing and roasting at 500oC. The treated
samples were investigated for metals bioleaching using
Acidithiobacillus ferrooxidans in batch reactors and the leaching
efficiencies were compared. It was found out that acetone washed
spent catalysts results in better metal recovery compare to roasted
spent. About 83% Ni, 20% Al, 50% Mo and 73% V were leached
using the acetone washed spent catalyst. In both the cases, Ni, V and
Mo was high compared to Al.
Abstract: Ionic liquids are well known as green solvents, reaction media and catalysis. Here, three different sulfonic acid functional ionic liquids prepared in the laboratory are used as catalysts in alkylation of p-cresol with tert-butyl alcohol. The kinetics on each of the catalysts was compared and a kinetic model was developed based on the product distribution over these catalysts. The kinetic parameters were estimated using Marquadt's algorithm to minimize the error function. The Arrhenius plots show a curvature which is best interpreted by the extended Arrhenius equation.