Abstract: Due to the concerns about the depletion of fossil fuel sources and the deteriorating environment, the attempt to investigate the production of renewable energy will play a crucial role as a potential to alleviate the dependency on mineral fuels. One particular area of interest is generation of bio-oil through sewage sludge (SS) pyrolysis. SS can be a potential candidate in contrast to other types of biomasses due to its availability and low cost. However, the presence of high molecular weight hydrocarbons and oxygenated compounds in the SS bio-oil hinders some of its fuel applications. In this context, catalytic pyrolysis is another attainable route to upgrade bio-oil quality. Among different catalysts (i.e., zeolites) studied for SS pyrolysis, activated chars (AC) are eco-friendly alternatives. The beneficial features of AC derived from SS comprise the comparatively large surface area, porosity, enriched surface functional groups and presence of a high amount of metal species that can improve the catalytic activity. Hence, a sludge-based AC catalyst was fabricated in a single-step pyrolysis reaction with NaOH as the activation agent and was compared with HZSM5 zeolite in this study. The thermal decomposition and kinetics were invested via thermogravimetric analysis (TGA) for guidance and control of pyrolysis and catalytic pyrolysis and the design of the pyrolysis setup. The results indicated that the pyrolysis and catalytic pyrolysis contain four obvious stages and the main decomposition reaction occurred in the range of 200-600 °C. Coats-Redfern method was applied in the 2nd and 3rd devolatilization stages to estimate the reaction order and activation energy (E) from the mass loss data. The average activation energy (Em) values for the reaction orders n = 1, 2 and 3 were in the range of 6.67-20.37 kJ/mol for SS; 1.51-6.87 kJ/mol for HZSM5; and 2.29-9.17 kJ/mol for AC, respectively. According to the results, AC and HZSM5 both were able to improve the reaction rate of SS pyrolysis by abridging the Em value. Moreover, to generate and examine the effect of the catalysts on the quality of bio-oil, a fixed-bed pyrolysis system was designed and implemented. The composition analysis of the produced bio-oil was carried out via gas chromatography/mass spectrometry (GC/MS). The selected SS to catalyst ratios were 1:1, 2:1 and 4:1. The optimum ratio in terms of cracking the long-chain hydrocarbons and removing oxygen-containing compounds was 1:1 for both catalysts. The upgraded bio-oils with HZSM5 and AC were in the total range of C4-C17 with around 72% in the range of C4-C9. The bio-oil from pyrolysis of SS contained 49.27% oxygenated compounds while the presence of HZSM5 and AC dropped to 7.3% and 13.02%, respectively. Meanwhile, generation of value-added chemicals such as light aromatic compounds were significantly improved in the catalytic process. Furthermore, the fabricated AC catalyst was characterized by BET, SEM-EDX, FT-IR and TGA techniques. Overall, this research demonstrated that AC is an efficient catalyst in the pyrolysis of SS and can be used as a cost-competitive catalyst in contrast to HZSM5.
Abstract: Acid leaching of flotation concentrate of oxide copper ore containing mainly of malachite was performed in a standard agitation tank with various parameters. The effects of solid to liquid ratio, sulfuric acid concentration, agitation speed, leaching temperature and time were examined to get proper conditions. The best conditions are 1:8 solid to liquid ratio, 10% concentration by weight, 250 rev/min, 30 oC and 5-min leaching time in respect. About 20% Cu grade assayed by atomic absorption technique with 98% copper recovery was obtained from these combined optimum conditions. Dissolution kinetics of the concentrate was approximated as a logarithmic function. As a result, the first-order reaction rate is suggested from this leaching study.
Abstract: Combustion of biomass is a promising alternative to reduce the high pollutant emission levels associated to the combustion of fossil flues due to the net null emission of CO2 attributed to biomass. However, the biomass selected should also have low contents of nitrogen and sulfur to limit the NOx and SOx emissions derived from its combustion. In this sense, olive stone is an excellent fuel to power combustion reactors with reduced levels of pollutant emissions. In this work, the combustion of olive stone particles is analyzed experimentally in a thermogravimetric analyzer (TGA) and in a bubbling fluidized bed reactor (BFB). The bubbling fluidized bed reactor was installed over a scale, conforming a macro-TGA. In both equipment, the evolution of the mass of the samples was registered as the combustion process progressed. The results show a much faster combustion process in the bubbling fluidized bed reactor compared to the thermogravimetric analyzer measurements, due to the higher heat transfer coefficient and the abrasion of the fuel particles by the bed material in the BFB reactor.
Abstract: Combustion analysis of suspended sodium droplet is performed by solving numerically the Navier-Stokes equations and the energy conservation equations. The combustion model consists of the pre-ignition and post-ignition models. The reaction rate for the pre-ignition model is based on the chemical kinetics, while that for the post-ignition model is based on the mass transfer rate of oxygen. The calculated droplet temperature is shown to be in good agreement with the existing experimental data. The temperature field in and around the droplet is obtained as well as the droplet shape variation, and the present numerical model is confirmed to be effective for the combustion analysis.
Abstract: The evolution of the pyrolysis of sewage sludge in a fixed and a fluidized bed was analyzed using a novel measuring technique. This original measuring technique consists of installing the whole reactor over a precision scale, capable of measuring the mass of the complete reactor with enough precision to detect the mass released by the sewage sludge sample during its pyrolysis. The inert conditions required for the pyrolysis process were obtained supplying the bed with a nitrogen flowrate, and the bed temperature was adjusted to either 500 ºC or 600 ºC using a group of three electric resistors. The sewage sludge sample was supplied through the top of the bed in a batch of 10 g. The measurement of the mass released by the sewage sludge sample was employed to determine the evolution of the reaction rate during the pyrolysis, the total amount of volatile matter released, and the pyrolysis time. The pyrolysis tests of sewage sludge in the fluidized bed were conducted using two different bed materials of the same size but different densities: silica sand and sepiolite particles. The higher density of silica sand particles induces a flotsam behavior for the sewage sludge particles which move close to the bed surface. In contrast, the lower density of sepiolite produces a neutrally-buoyant behavior for the sewage sludge particles, which shows a proper circulation throughout the whole bed in this case. The analysis of the evolution of the pyrolysis process in both fluidized beds show that the pyrolysis is faster when buoyancy effects are negligible, i.e. in the bed conformed by sepiolite particles. Moreover, sepiolite was found to show an absorbent capability for the volatile matter released during the pyrolysis of sewage sludge.
Abstract: In this work, a new composite adsorbent based on a mesoporous silica SBA-15 with platelet morphology and tin salt of tungstomolybdophosphoric (TWMP) acid was synthesized and applied for uranium adsorption from aqueous solution. The sample was characterized by X-ray diffraction, Fourier transfer infra-red, and N2 adsorption-desorption analysis, and then, effect of various parameters such as concentration of metal ions and contact time on adsorption behavior was examined. The experimental result showed that the adsorption process was explained by the Langmuir isotherm model very well, and predominant reaction mechanism is physisorption. Kinetic data of adsorption suggest that the adsorption process can be described by the pseudo second-order reaction rate model.
Abstract: The main objective of this research was to study the differences of aluminum hydrolytic products between two PACl preparation methods. These two methods were the acidification process of freshly formed amorphous Al(OH)3 and the conventional alkalization process of aluminum chloride solution. According to Ferron test and 27Al NMR analysis of those two PACl preparation procedures, the reaction rate constant (k) values and Al13 percentage of acid addition process at high basicity value were both lower than those values of the alkaline addition process. The results showed that the molecular structure and size distribution of the aluminum species in both preparing methods were suspected to be significantly different at high basicity value.
Abstract: One of the main characteristics of Heavy Water Moderated Reactors is their high production of plutonium. This article demonstrates the possibility of reduction of plutonium and other actinides in Heavy Water Research Reactor. Among the many ways for reducing plutonium production in a heavy water reactor, in this research, changing the fuel from natural Uranium fuel to Thorium-Uranium mixed fuel was focused. The main fissile nucleus in Thorium-Uranium fuels is U-233 which would be produced after neutron absorption by Th-232, so the Thorium-Uranium fuels have some known advantages compared to the Uranium fuels. Due to this fact, four Thorium-Uranium fuels with different compositions ratios were chosen in our simulations; a) 10% UO2-90% THO2 (enriched= 20%); b) 15% UO2-85% THO2 (enriched= 10%); c) 30% UO2-70% THO2 (enriched= 5%); d) 35% UO2-65% THO2 (enriched= 3.7%). The natural Uranium Oxide (UO2) is considered as the reference fuel, in other words all of the calculated data are compared with the related data from Uranium fuel. Neutronic parameters were calculated and used as the comparison parameters. All calculations were performed by Monte Carol (MCNPX2.6) steady state reaction rate calculation linked to a deterministic depletion calculation (CINDER90). The obtained computational data showed that Thorium-Uranium fuels with four different fissile compositions ratios can satisfy the safety and operating requirements for Heavy Water Research Reactor. Furthermore, Thorium-Uranium fuels have a very good proliferation resistance and consume less fissile material than uranium fuels at the same reactor operation time. Using mixed Thorium-Uranium fuels reduced the long-lived α emitter, high radiotoxic wastes and the radio toxicity level of spent fuel.
Abstract: The kinetics of the oxidation of amitriptyline (AT) by sodium N-bromotoluene sulphonamide (C6H5SO2NBrNa) has been studied in an acidic buffer medium of pH 1.2 at 303 K. The oxidation reaction of AT was followed spectrophotometrically at maximum wavelength, 410 nm. The reaction rate shows a first order dependence each on concentration of AT and concentration of sodium N-bromotoluene sulphonamide. The reaction also shows an inverse fractional order dependence at low or high concentration of HCl. The dielectric constant of the solvent shows negative effect on the rate of reaction. The addition of halide ions and the reduction product of BAT have no significant effect on the rate. The rate is unchanged with the variation in the ionic strength (NaClO4) of the medium. Addition of reaction mixtures to be aqueous acrylamide solution did not initiate polymerization, indicating the absence of free radical species. The stoichiometry of the reaction was found to be 1:1 and oxidation product of AT is identified. The Michaelis-Menton type of kinetics has been proposed. The CH3C6H5SO2NHBr has been assumed to be the reactive oxidizing species. Thermodynamical parameters were computed by studying the reactions at different temperatures. A mechanism consistent with observed kinetics is presented.
Abstract: Recovering resources from water purification sludge
(WPS) have been gradually stipulated in environmental protection
laws and regulations in many nations. Hence, reusing the WPS is
becoming an important topic, and recovering alum from WPS is one of
the many practical alternatives. Most previous research efforts have
been conducted on studying the amphoteric characteristic of aluminum
hydroxide for investigating the optimum pH range to dissolve the
Al(III) species from WPS, but it has been lack of reaction kinetics or
mechanisms related discussion. Therefore, in this investigation, water
purification sludge (WPS) solution was broken by ultrasound to make
particle size of reactants smaller, specific surface area larger.
According to the reaction kinetics, these phenomena let the dissolved
aluminum salt quantity increased and the reaction rate go faster.
Abstract: Amoxicillin is an antibiotic which is widely used to
treat various infections in both human beings and animals. However,
when amoxicillin is released into the environment, it is a major
problem. Amoxicillin causes bacterial resistance to these drugs and
failure of treatment with antibiotics. Liquid membrane is of great
interest as a promising method for the separation and recovery of the
target ions from aqueous solutions due to the use of carriers for the
transport mechanism, resulting in highly selectivity and rapid
transportation of the desired metal ions. The simultaneous processes
of extraction and stripping in a single unit operation of liquid
membrane system are very interesting. Therefore, it is practical to
apply liquid membrane, particularly the HFSLM for industrial
applications as HFSLM is proved to be a separation process with
lower capital and operating costs, low energy and extractant with
long life time, high selectivity and high fluxes compared with solid
membranes. It is a simple design amenable to scaling up for industrial
applications. The extraction and recovery for (Amoxicillin) through
the hollow fiber supported liquid membrane (HFSLM) using
aliquat336 as a carrier were explored with the experimental data. The
important variables affecting on transport of amoxicillin viz.
extractant concentration and operating time were investigated. The
highest AMOX- extraction percentages of 85.35 and Amoxicillin
stripping of 80.04 were achieved with the best condition at 6 mmol/L
[aliquat336] and operating time 100 min. The extraction reaction
order (n) and the extraction reaction rate constant (kf) were found to
be 1.00 and 0.0344 min-1, respectively.
Abstract: Incineration of municipal solid waste (MSW) is one of
the key scopes in the global clean energy strategy. A computational
fluid dynamics (CFD) model was established in order to reveal these
features of the combustion process in a fixed porous bed of MSW.
Transporting equations and process rate equations of the waste bed
were modeled and set up to describe the incineration process,
according to the local thermal conditions and waste property
characters. Gas phase turbulence was modeled using k-ε turbulent
model and the particle phase was modeled using the kinetic theory of
granular flow. The heterogeneous reaction rates were determined
using Arrhenius eddy dissipation and the Arrhenius-diffusion
reaction rates. The effects of primary air flow rate and temperature in
the burning process of simulated MSW are investigated
experimentally and numerically. The simulation results in bed are
accordant with experimental data well. The model provides detailed
information on burning processes in the fixed bed, which is otherwise
very difficult to obtain by conventional experimental techniques.
Abstract: A computational fluid dynamics (CFD) model is
developed for rechargeable non-aqueous electrolyte lithium-air
batteries with a partial opening for oxygen supply to the cathode.
Multi-phase transport phenomena occurred in the battery are
considered, including dissolved lithium ions and oxygen gas in the
liquid electrolyte, solid-phase electron transfer in the porous
functional materials and liquid-phase charge transport in the
electrolyte. These transport processes are coupled with the
electrochemical reactions at the active surfaces, and effects of
discharge reaction-generated solid Li2O2 on the transport properties
and the electrochemical reaction rate are evaluated and implemented
in the model. The predicted results are discussed and analyzed in terms
of the spatial and transient distribution of various parameters, such as
local oxygen concentration, reaction rate, variable solid Li2O2 volume
fraction and porosity, as well as the effective diffusion coefficients. It
is found that the effect of the solid Li2O2 product deposited at the solid
active surfaces is significant on the transport phenomena and the
overall battery performance.
Abstract: Nanoscale thermites such as the composite mixture of
nano-sized aluminum and molybdenum trioxide powders possess
several technical advantages such as much higher reaction rate and
shorter ignition delay, when compared to the conventional energetic
formulations made of micron-sized metal and oxidizer particles. In this
study, the self-propagation of combustion wave in compacted pellets
of nanoscale thermite composites is modeled and computationally
investigated by utilizing the activation energy reduction of aluminum
particles due to nanoscale particle sizes. The present computational
model predicts the speed of combustion wave propagation which is
good agreement with the corresponding experiments of thermite
reaction. Also, several characteristics of thermite reaction in nanoscale
composites are discussed including the ignition delay and combustion
wave structures.
Abstract: A theoretical approach to consider formation of chemical compound layer at the interface between initial substances A and B due to the interfacial interaction and diffusion is developed. It is considered situation when speed of interfacial interaction is large enough and diffusion of A-atoms through AB-layer is much more then diffusion of B-atoms. Atoms from A-layer diffuse toward B-atoms and form AB-atoms on the surface of B-layer. B-atoms are assumed to be immobile. The growth kinetics of the AB-layer is described by two differential equations with non-linear coupling, producing a good fit to the experimental data. It is shown that growth of the thickness of the AB-layer determines by dependence of chemical reaction rate on reactants concentration. In special case the thickness of the AB-layer can grow linearly or parabolically depending on that which of processes (interaction or the diffusion) controls the growth. The thickness of AB-layer as function of time is obtained. The moment of time (transition point) at which the linear growth are changed by parabolic is found.
Abstract: Ozone is well known as a powerful, fast reacting oxidant. Ozone based processes produce no by-product residual as non-reacted ozone decomposes to molecular oxygen. Therefore an application of ozone is widely accepted as one of the main approaches for a Sustainable and Clean Technologies development.
There are number of technologies which require ozone to be delivered to specific points of a production network or reactors construction. Due to space constraints, high reactivity and short life time of ozone the use of ozone generators even of a bench top scale is practically limited. This requires development of mini/micro scale ozone generator which can be directly incorporated into production units.
Our report presents a feasibility study of a new micro scale rector for ozone generation (MROG). Data on MROG calibration and indigo decomposition at different operation conditions are presented.
At selected operation conditions with residence time of 0.25 s the process of ozone generation is not limited by reaction rate and the amount of ozone produced is a function of power applied. It was shown that the MROG is capable to produce ozone at voltage level starting from 3.5kV with ozone concentration of 5.28*10-6 (mol/L) at 5kV. This is in line with data presented on numerical investigation for a MROG. It was shown that in compare to a conventional ozone generator, MROG has lower power consumption at low voltages and atmospheric pressure.
The MROG construction makes it applicable for both submerged and dry systems. With a robust compact design MROG can be used as an integrated module for production lines of high complexity.
Abstract: In the present study, two distinctly different approaches are followed for modeling of reactive distillation column, the equilibrium stage model and the nonequilibrium stage model. These models are simulated with a computer code developed in the present
study using MATLAB programming. In the equilibrium stage models, the vapor and liquid phases are assumed to be in equilibrium and allowance is made for finite reaction rates, where as in the nonequilibrium stage models simultaneous mass transfer and reaction rates are considered. These simulated model results are validated from the experimental data reported in the literature. The simulated results of equilibrium and nonequilibrium models are compared for concentration, temperature and reaction rate profiles in a reactive distillation column for Methyl Tert Butyle Ether (MTBE) production. Both the models show similar trend for the concentration, temperature and reaction rate profiles but the nonequilibrium model predictions are higher and closer to the experimental values reported in the literature.
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 have 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 22.1MPa), 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 conditions is investigated with the use of Ru/Al2O3 catalyst. 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.
The catalytic gasification experiments were made with five different reaction temperatures (400, 450, 500, 550 and 600°C) and five reaction times (30, 60, 90, 120 and 150s), under a constant pressure of 25MPa. Through these experiments, the effects of reaction temperature and time on the gasification yield, gaseous product composition and OMW treatment efficiency were investigated.
Abstract: The equilibrium process of plasma nitrogen species by
chemical kinetic reactions along various pressures is successfully
investigated. The equilibrium process is required in industrial
application to obtain the stable condition when heating up the
material for having homogenous reaction. Nitrogen species densities
is modeled by a continuity equation and extended Arrhenius form.
These equations are used to integrate the change of density over the
time. The integration is to acquire density and the reaction rate of
each reaction where temperature and time dependence are imposed.
A comparison is made with global model within pressure range of 1-
100mTorr and the temperature of electron is set to be higher than
other nitrogen species. The results shows that the chemical kinetic
model only agrees for high pressure because of no power imposed;
while the global model considers the external power along the
pressure range then the electron and nitrogen species give highly
quantity densities by factor of 3 to 5.
Abstract: An effort has been taken to simulate the combustion
and performance characteristics of biodiesel fuel in direct injection
(D.I) low heat rejection (LHR) diesel engine. Comprehensive
analyses on combustion characteristics such as cylinder pressure,
peak cylinder pressure, heat release and performance characteristics
such as specific fuel consumption and brake thermal efficiency are
carried out. Compression ignition (C.I) engine cycle simulation was
developed and modified in to LHR engine for both diesel and
biodiesel fuel. On the basis of first law of thermodynamics the
properties at each degree crank angle was calculated. Preparation and
reaction rate model was used to calculate the instantaneous heat
release rate. A gas-wall heat transfer calculations are based on the
ANNAND-s combined heat transfer model with instantaneous wall
temperature to analyze the effect of coating on heat transfer. The
simulated results are validated by conducting the experiments on the
test engine under identical operating condition on a turbocharged D.I
diesel engine. In this analysis 20% of biodiesel (derived from
Jatropha oil) blended with diesel and used in both conventional and
LHR engine. The simulated combustion and performance
characteristics results are found satisfactory with the experimental
value.