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: Different agricultural waste peels were assessed for
their suitability to be used as primary substrates for the
bioremediation of free cyanide (CN-) by a cyanide-degrading fungus
Aspergillus awamori isolated from cyanide containing wastewater.
The bioremediated CN- concentration were in the range of 36 to 110
mg CN-/L, with Orange (C. sinensis) > Carrot (D. carota) > Onion
(A. cepa) > Apple (M. pumila), being chosen as suitable substrates
for large scale CN- degradation processes due to: 1) the high
concentration of bioremediated CN-, 2) total reduced sugars released
into solution to sustain the biocatalyst, and 3) minimal residual NH4-
N concentration after fermentation. The bioremediation rate constants
(k) were 0.017h-1 (0h < t < 24h), with improved bioremediation rates
(0.02189h-1) observed after 24h. The averaged nitrilase activity was
~10 U/L.
Abstract: Biodiesel is traditionally produced from oleaginous
plants. On the other hand, increasing biodiesel production from these
raw materials could create problems of food supply. Producing
biodiesel from microalgae could help to overcome this difficulty,
because microalgae are rich in lipids and do not compete for arable
lands. However, no studies had compared vegetable and microalgae
oil-based biodiesel in terms of yield, viscosity and heat of
combustion. In the present study, commercial canola and microalgae
oil were therefore transesterified with methanol under a homogenous
alkali catalyst (potassium hydroxide) at 100oC for 1h. The result
showed that microalgae-based oil has a higher yield in biodiesel with
89.7% (g biodiesel/g oil) and a lower kinematic viscosity (22oC) of
4.31 mm/s2 than canola oil.
Abstract: Biodisel is a type of biofuel having similar properties of diesel fuel but lacks substances (undesirable emissions) such as sulfur, nitrogen and aromatic polycyclic. Upon filtration of waste oil, the biodiesel fuel was produced via carrying out transestrification reaction of triglycerides followed by conducting viscosity, density, flash point, cloud point, pour point and copper strip corrosion tests on the samples and comparing with EN14214 and ASTM 6751 standards and all results were found in the permitted limit. The highest yield of biodiesel production reaction was found 46.6435 g when Sodium Hydroxide catalyst in amount of 0.375g was employed, 44.2347 g when Sodium methoxide catalyst in amount of 0.5g was employed and 56.5124 g when acid sulfuric catalyst in amount of 1g was employed and 47.3290 g when two stage reaction was done.
Abstract: The catalytic dehydroxylation of glycerol to propylene
glycol was investigated over Cu-ZnO/Al2O3 prepared by incipient
wetness impregnation (IWI) method with different purity feedstocks -
refined glycerol and technical grade glycerol. The main purpose is to
investigate the effects of feed impurities that cause the catalyst
deactivation. The prepared catalyst were tested for its catalytic
activity and selectivity in a continuous flow fixed bed reactor at 523
K, 500 psig, H2/feed molar ratio of 4 and WHSV of 3 h-1. The results
showed that conversion of refined glycerol and technical grade
glycerol at time on stream 6 hour are 99% and 71% and selectivity to
propylene glycol are 87% and 56% respectively. The ICP-EOS and
TPO results indicated that the cause of catalyst deactivation was the
amount of impurities in the feedstock. The higher amount of
impurities (especially Na and K) the lower catalytic activity.
Abstract: The accelerated sonophotocatalytic degradation of
Reactive Red (RR) 120 dye under visible light using dye sensitized
TiO2 activated by ultrasound has been carried out. The effect of
sonolysis, photocatalysis and sonophotocatalysis under visible light
has been examined to study the influence on the degradation rates by
varying the initial substrate concentration, pH and catalyst loading to
ascertain the synergistic effect on the degradation techniques.
Ultrasonic activation contributes degradation through cavitation
leading to the splitting of H2O2 produced by both photocatalysis and
sonolysis. This results in the formation of oxidative species, such as
singlet oxygen (1O2) and superoxide (O2
-●) radicals in the presence of
oxygen. The increase in the amount of reactive radical species which
induce faster oxidation of the substrate and degradation of
intermediates and also the deaggregation of the photocatalyst are
responsible for the synergy observed under sonication. A
comparative study of photocatalysis and sonophotocatalysis using
TiO2, Hombikat UV 100 and ZnO was also carried out.
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: Hydrothermally synthesized high silica borosilicates
with the MFI structure was subjected to several characterization
techniques. The effect of boron on the structure and acidity of
HZSM-5 catalyst were studied by XRD, SEM, N2 adsorption, solid
state NMR, NH3-TPD. It was confirmed that boron had entered the
framework in the boron samples. The results also revealed that strong
acidity was weakened and weak acidity was strengthened by the
boron added zeolite framework compared with parent catalyst. The
catalytic performance was carried out in a fixed bed at 460°C for
methanol to propylene (MTP) reaction. The results of MTP reaction
showed a great increment of the propylene selectivity and excellent
stability for the B-HZSM-5. The catalyst exhibited about 81%
selectivity to C2
= - C4
= olefins with 40% selectivity of propylene as
major component at near 100% methanol conversion, and the stable
performance in the studied period was 100h.
Abstract: All around the world pulp and paper industries are the
biggest plant production with the environmental pollution as the
biggest challenge facing the pulp manufacturing operations. The
concern among these industries is to produce a high volume of papers
with the high quality standard and of low cost without affecting the
environment. This result obtained from this bleaching study show
that the activation of peroxide was an effective method of reducing
the total applied charge of chlorine dioxide which is harmful to our
environment and also show that softwood and hardwood Kraft pulps
responded linearly to the peroxide treatments. During the bleaching
process the production plant produce chlorines. Under the trial stages
chloride dioxide has been reduced by 3 kg/ton to reduce the
brightness from 65% ISO to 60% ISO of pulp and the dosing point
returned to the E stage charges by pre-treating Kraft pulps with
hydrogen peroxide. The pulp and paper industry has developed
elemental chlorine free (ECF) and totally chlorine free (TCF)
bleaching, in their quest for being environmental friendly, they have
been looking at ways to turn their ECF process into a TCF process
while still being competitive. This prompted the research to
investigate the capability of the hydrogen peroxide as catalyst to
reduce chloride dioxide.
Abstract: Enzymatic saccharification of biomass for reducing
sugar production is one of the crucial processes in biofuel production
through biochemical conversion. In this study, enzymatic
saccharification of dilute potassium hydroxide (KOH) pre-treated
Tetraselmis suecica biomass was carried out by using cellulase
enzyme obtained from Trichoderma longibrachiatum. Initially, the
pre-treatment conditions were optimised by changing alkali reagent
concentration, retention time for reaction, and temperature. The T.
suecica biomass after pre-treatment was also characterized using
Fourier Transform Infrared Spectra and Scanning Electron
Microscope. These analyses revealed that the functional group such
as acetyl and hydroxyl groups, structure and surface of T. suecica
biomass were changed through pre-treatment, which is favourable for
enzymatic saccharification process. Comparison of enzymatic
saccharification of untreated and pre-treated microalgal biomass
indicated that higher level of reducing sugar can be obtained from
pre-treated T. suecica. Enzymatic saccharification of pre-treated T.
suecica biomass was optimised by changing temperature, pH, and
enzyme concentration to solid ratio ([E]/[S]). Highest conversion of
carbohydrate into reducing sugar of 95% amounted to reducing sugar
yield of 20 (wt%) from pre-treated T. suecica was obtained from
saccharification, at temperature: 40°C, pH: 4.5 and [E]/[S] of 0.1
after 72 h of incubation. Hydrolysate obtained from enzymatic
saccharification of pretreated T. suecica biomass was further
fermented into biobutanol using Clostridium saccharoperbutyliticum
as biocatalyst. The results from this study demonstrate a positive
prospect of application of dilute alkaline pre-treatment to enhance
enzymatic saccharification and biobutanol production from
microalgal biomass.
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: Transesterification of candlenut (aleurites moluccana)
oil with methanol using potassium hydroxide as catalyst was
studied. The objective of the present investigation was to produce
the methyl ester for use as biodiesel. The operation variables
employed were methanol to oil molar ratio (3:1 – 9:1), catalyst
concentration (0.50 – 1.5 %) and temperature (303 – 343K). Oil
volume of 150 mL, reaction time of 75 min were fixed as common
parameters in all the experiments. The concentration of methyl ester
was evaluated by mass balance of free glycerol formed which was
analyzed by using periodic acid. The optimal triglyceride conversion
was attained by using methanol to oil ratio of 6:1, potassium
hydroxide as catalyst was of 1%, at room temperature. Methyl ester
formed was characterized by its density, viscosity, cloud and pour
points. The biodiesel properties had properties similar to those of
diesel oil, except for the viscosity that was higher.
Abstract: A large number of chemical, bio-chemical and pollution-control processes use heterogeneous fixed-bed reactors. The use of finite hollow cylindrical catalyst pellets can enhance conversion levels in such reactors. The absence of the pellet core can significantly lower the diffusional resistance associated with the solid phase. This leads to a better utilization of the catalytic material, which is reflected in the higher values for the effectiveness factor, leading ultimately to an enhanced conversion level in the reactor. It is however important to develop a rigorous heterogeneous model for the reactor incorporating the two-dimensional feature of the solid phase owing to the presence of the finite hollow cylindrical catalyst pellet. Presently, heterogeneous models reported in the literature invariably employ one-dimension solid phase models meant for spherical catalyst pellets. The objective of the paper is to present a rigorous model of the fixed-bed reactors containing finite hollow cylindrical catalyst pellets. The reaction kinetics considered here is the widely used Michaelis–Menten kinetics for the liquid-phase bio-chemical reactions. The reaction parameters used here are for the enzymatic degradation of urea. Results indicate that increasing the height to diameter ratio helps to improve the conversion level. On the other hand, decreasing the thickness is apparently not as effective. This could however be explained in terms of the higher void fraction of the bed that causes a smaller amount of the solid phase to be packed in the fixed-bed bio-chemical reactor.
Abstract: Biodiesel production with used frying by
transesterification reaction with methanol, using a commercial
kaolinite thermally-activated solid acid catalyst was investigated.
The surface area, the average pore diameter and pore volume of the
kaolinite catalyst were 10 m2/g, 13.0 nm and 30 mm3/g, respectively.
The optimal conditions for the transesterification reaction were
determined to be oil/methanol, in a molar ratio 1:31, temperature 160
ºC and catalyst concentration of 3% (w/w). The yield of fatty acids
methyl esters (FAME) was 92.4% after 2 h of reaction. This method
of preparation of biodiesel can be a positive alternative for utilizing
used frying corn oil for feedstock of biodiesel combined with the
inexpensive catalyst.
Abstract: Hydrogenated biodiesel is one of the most promising
renewable fuels. It has many advantages over conventional biodiesel,
including higher cetane number, higher heating value, lower
viscosity, and lower corrosiveness due to its absence of oxygen.
From previous work, Pd/TiO2 gave high conversion and selectivity in
hydrogenated biodiesel. In this work, the effect of biomass feedstocks
(i.e. beef fat, chicken fat, pork fat, and jatropha oil) on the production
of hydrogenated biodiesel over Pd/TiO2 has been studied. Biomass
feedstocks were analyzed by ICP-OES (inductively coupled plasma
optical emission spectrometry) to identify the content of impurities
(i.e. P, K, Ca, Na, and Mg). The deoxygenation catalyst, Pd/TiO2,
was prepared by incipient wetness impregnation (IWI) and tested in a
continuous flow packed-bed reactor at 500 psig, 325°C, H2/feed
molar ratio of 30, and LHSV of 4 h-1 for its catalytic activity and
selectivity in hydrodeoxygenation. All feedstocks gave high
selectivity in diesel specification range hydrocarbons and the main
hydrocarbons were n-pentadecane (n-C15) and n-heptadecane (n-
C17), resulting from the decarbonylation/decarboxylation reaction.
Intermediates such as oleic acid, stearic acid, palmitic acid, and esters
were also detected in minor amount. The conversion of triglycerides
in jatropha oil is higher than those of chicken fat, pork fat, and beef
fat, respectively. The higher concentration of metal impurities in
feedstock, the lower conversion of feedstock.
Abstract: Heterogeneous catalysis is vital for a number of
chemical, refinery and pollution control processes. The use of
catalyst pellets of hollow cylindrical shape provide several distinct
advantages over other common shapes, and can therefore help to
enhance conversion levels in reactors. A better utilization of the
catalytic material is probably most notable of these features due to
the absence of the pellet core, which helps to significantly lower the
effect of the internal transport resistance. This is reflected in the
enhancement of the effectiveness factor. For the case of the first order
irreversible kinetics, a substantial increase in the effectiveness factor
can be obtained by varying shape parameters. Important shape
parameters of a finite hollow cylinder are the ratio of the inside to the
outside radii (κ) and the height to the diameter ratio (γ). A high value
of κ the generally helps to enhance the effectiveness factor. On the
other hand, lower values of the effectiveness factors are obtained
when the dimension of the height and the diameter are comparable.
Thus, the departure of parameter γ from the unity favors higher
effectiveness factor. Since a higher effectiveness factor is a measure
of a greater utilization of the catalytic material, higher conversion
levels can be achieved using the hollow cylindrical pellets possessing
optimized shape parameters.
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.