Abstract: Bioleaching of spent catalyst using moderate thermophilic chemolithotrophic acidophiles in growth medium without Fe source was investigated with two different pulp densities and three different size fractions. All the experiments were conducted on shake flasks at a temperature of 65 °C. The leaching yield of Ni and Al was found to be promising with very high leaching yield of 92-96% followed by Al as 41-76%, which means both Ni and Al leaching were favored by the moderate thermophilic bioleaching compared to the mesophilic bioleaching. The acid consumption was comparatively higher for the 10% pulp density experiments. Comparatively minimal difference in the leaching yield with different size fractions and different pulp densities show no requirement of grinding and using low pulp density less than 10%. This process would rather be economical as well as eco-friendly process for future optimization of the recovery of metal values from spent catalyst.
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: 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: 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: 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: 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: Renewable energy sources have gained ultimate urgency due to the need of the preservation of the environment for a sustainable development. Pyrolysis is an ultimate promising process in the recycling and acquisition of precious chemicals from wastes. Here, the co-pyrolysis of hazelnut shell with ultra-high molecular weight polyethylene was carried out catalytically and noncatalytically at 500 and 650 ºC. Potassium dichromate was added in certain amounts to act as a catalyst. The liquid, solid and gas products quantities were determined by gravimetry. As a main result, remarkable increases in gasification were observed by using this catalyst for pure components and their blends especially at 650 ºC. The increase in gas product quantity was compensated mainly with the decreases in the solid products and additionally in some cases liquid products quantities. These observations may stem from mainly the activation of carbon-carbon bonds rather than carbon-hydrogen bonds via potassium dichromate. Also, the catalytic effect of potassium dichromate on HS: PEO and HS: UHMWPE co-pyrolysis was compared.
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: Transesterified vegetable oils (biodiesel) are promising alternative fuel for diesel engines. Used vegetable oils are disposed from restaurants in large quantities. But higher viscosity restricts their direct use in diesel engines. In this study, used cooking oil was dehydrated and then transesterified using an alkaline catalyst. The combustion, performance and emission characteristics of Used Cooking oil Methyl Ester (UCME) and its blends with diesel oil are analysed in a direct injection C.I. engine. The fuel properties and the combustion characteristics of UCME are found to be similar to those of diesel. A minor decrease in thermal efficiency with significant improvement in reduction of particulates, carbon monoxide and unburnt hydrocarbons is observed compared to diesel. The use of transesterified used cooking oil and its blends as fuel for diesel engines will reduce dependence on fossil fuels and also decrease considerably the environmental pollution.
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: Silver nano-particles have been used for antibacterial
purpose and it is also believed to have removal of odorous compounds,
oxidation capacity as a metal catalyst. In this study, silver
nano-particles in nano sizes (5-30 nm) were prepared on the surface of
NaHCO3, the supporting material, using a sputtering method that
provided high silver content and minimized conglomerating problems
observed in the common AgNO3 photo-deposition method. The silver
nano-particles were dispersed by dissolving Ag-NaHCO3 into water,
and the dispersed silver nano-particles in the aqueous phase were
applied to remove inorganic odor compounds, H2S, in a scrubbing
reactor. Hydrogen sulfide in the gas phase was rapidly removed by the
silver nano-particles, and the concentration of sulfate (SO4
2-) ion
increased with time due to the oxidation reaction by silver as a
catalyst. Consequently, the experimental results demonstrated that the
silver nano-particles in the aqueous solution can be successfully
applied to remove odorous compounds without adding additional
energy sources and producing any harmful byproducts
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 kinetics of palm oil catalytic cracking over
aluminum containing mesoporous silica Al-MCM-41 (5% Al) was
investigated in a batch autoclave reactor at the temperatures range of
573 – 673 K. The catalyst was prepared by using sol-gel technique
and has been characterized by nitrogen adsorption and x-ray
diffraction methods. Surface area of 1276 m2/g with average pore
diameter of 2.54 nm and pore volume of 0.811 cm3/g was obtained.
The experimental catalytic cracking runs were conducted using 50 g
of oil and 1 g of catalyst. The reaction pressure was recorded at
different time intervals and the data were analyzed using Levenberg-
Marquardt (LM) algorithm using polymath software. The results
show that the reaction order was found to be -1.5 and activation
energy of 3200 J/gmol.
Abstract: The present paper discusses the selection of process
parameters for obtaining optimal nanocrystallites size in the CuOZrO2
catalyst. There are some parameters changing the inorganic
structure which have an influence on the role of hydrolysis and
condensation reaction. A statistical design test method is
implemented in order to optimize the experimental conditions of
CuO-ZrO2 nanoparticles preparation. This method is applied for the
experiments and L16 orthogonal array standard. The crystallites size
is considered as an index. This index will be used for the analysis in
the condition where the parameters vary. The effect of pH, H2O/
precursor molar ratio (R), time and temperature of calcination,
chelating agent and alcohol volume are particularity investigated
among all other parameters. In accordance with the results of
Taguchi, it is found that temperature has the greatest impact on the
particle size. The pH and H2O/ precursor molar ratio have low
influences as compared with temperature. The alcohol volume as
well as the time has almost no effect as compared with all other
parameters. Temperature also has an influence on the morphology
and amorphous structure of zirconia. The optimal conditions are
determined by using Taguchi method. The nanocatalyst is studied by
DTA-TG, XRD, EDS, SEM and TEM. The results of this research
indicate that it is possible to vary the structure, morphology and
properties of the sol-gel by controlling the above-mentioned
parameters.
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: 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: Hydrogen is regarded to play an important role in
future energy systems because it can be produced from abundant
resources and its combustion only generates water. The disposal of
waste tyres is a major problem in environmental management
throughout the world. The use of waste materials as a source of
hydrogen is particularly of interest in that it would also solve a waste
treatment problem. There is much interest in the use of alternative
feedstocks for the production of hydrogen since more than 95% of
current production is from fossil fuels. The pyrolysis of waste tyres
for the production of liquid fuels, activated carbons and gases has
been extensively researched. However, combining pyrolysis with
gasification is a novel process that can gasify the gaseous products
from pyrolysis. In this paper, an experimental investigation into the
production of hydrogen and other gases from the bench scale
pyrolysis-gasification of tyres has been investigated. Experiments
were carried using a two stage system consisting of pyrolysis of the
waste tyres followed by catalytic steam gasification of the evolved
gases and vapours in a second reactor. Experiments were conducted
at a pyrolysis temperature of 500 °C using Ni/Al2O3 as a catalyst. The
results showed that there was a dramatic increase in gas yield and the
potential H2 production when the gasification temperature was
increased from 600 to 900 oC. Overall, the process showed that high
yields of hydrogen can be produced from waste tyres.
Abstract: Spent petroleum catalyst from Korean petrochemical
industry contains trace amount of metals such as Ni, V and Mo.
Therefore an attempt was made to recover those trace metal using
bioleaching process. Different leaching parameters such as Fe(II)
concentration, pulp density, pH, temperature and particle size of
spent catalyst particle were studied to evaluate their effects on the
leaching efficiency. All the three metal ions like Ni, V and Mo
followed dual kinetics, i.e., initial faster followed by slower rate. The
percentage of leaching efficiency of Ni and V were higher than Mo.
The leaching process followed a diffusion controlled model and the
product layer was observed to be impervious due to formation of
ammonium jarosite (NH4)Fe3(SO4)2(OH)6. In addition, the lower
leaching efficiency of Mo was observed due to a hydrophobic coating
of elemental sulfur over Mo matrix in the spent catalyst.