Abstract: Three emerging contaminants (amitriptyline hydrochloride, methyl salicylate and 2-phenoxyethanol) frequently found in waste-waters were selected to be individually degraded in ultra-pure water by the combined advanced oxidation process constituted by UV radiation and chlorine. The influence of pH, initial chlorine concentration and nature of the contaminants was firstly explored. The trend for the reactivity of the selected compounds was deduced: amitriptyline hydrochloride > methyl salicylate > 2-phenoxyethanol. A later kinetic study was carried out and focused on the specific evaluation of the first-order rate constants and the determination of the partial contribution to the global reaction of the direct photochemical pathway and the radical pathway. A comparison between the rate constant values among photochemical experiments without and with the presence of Cl2 reveals a clear increase in the oxidation efficiency of the combined process with respect to the photochemical reaction alone. In a second stage, the simultaneous oxidation of mixtures of the selected contaminants in several types of water (ultrapure water, surface water from a reservoir, and two secondary effluents) was also performed by the same combination UV/Cl2 under more realistic operating conditions. The efficiency of this combined system UV/Cl2 was compared to other oxidants such as the UV/S2O82- and UV/H2O2 AOPs. Results confirmed that the UV/Cl2 system provides higher elimination efficiencies among the AOPs tested.
Abstract: The kinetics of Cu(II) transport through a bulk liquid membrane with different membrane materials was investigated in this work. Three types of membrane materials were used: fresh cooking oil, waste cooking oil and kerosene, each of which was mixed with di-2-ethylhexylphosphoric acid (carrier) and tributylphosphate (modifier). Kinetic models derived from the kinetic laws of two consecutive irreversible first-order reactions were used to study the facilitated transport of Cu(II) across the source, membrane and receiving phases of bulk liquid membrane. It was found that the transport kinetics of Cu(II) across the source phase was not affected by different types of membrane materials but decreased considerably when the membrane materials changed from kerosene, waste cooking oil to fresh cooking oil. The rate constants of Cu(II) removal and recovery processes through the bulk liquid membrane were also determined.
Abstract: Four phenylurea herbicides (isoproturon, chlortoluron, diuron and linuron) were dissolved in different water matrices in order to study their chemical degradation by using UV radiation, ozone and some advanced oxidation processes (UV/H2O2, O3/H2O2, Fenton reagent and the photo- Fenton system). The waters used were: ultra-pure water, a commercial mineral water, a groundwater and a surface water taken from a reservoir. Elimination levels were established for each herbicide and for several global quality parameters, and a kinetic study was performed in order to determine basic kinetic parameters of each reaction between the target phenylureas and these oxidizing systems.
Abstract: In this study, the kinetic of biogas production was studied by performing a series laboratory experiment using rumen fluid of animal ruminant as inoculums. Cattle manure as substrate was inoculated by rumen fluid to the anaerobic biodigester. Laboratory experiments using 400 ml biodigester were performed in batch operation mode. Given 100 grams of fresh cattle manure was fed to each biodigester and mixed with rumen fluid by manure : rumen weight ratio of 1:1 (MR11). The operating temperatures were varied at room temperature and 38.5 oC. The cumulative volume of biogas produced was used to measure the biodigester performance. The research showed that the rumen fluid inoculated to biodigester gave significant effect to biogas production (P
Abstract: Solutions are proposed for the central problem of estimating the reaction rate coefficients in homogeneous kinetics. The first is based upon the fact that the right hand side of a kinetic differential equation is linear in the rate constants, whereas the second one uses the technique of neural networks. This second one is discussed deeply and its advantages, disadvantages and conditions of applicability are analyzed in the mirror of the first one. Numerical analysis carried out on practical models using simulated data, and our programs written in Mathematica.
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: Thermo-chemical treatment (TCT) such as pyrolysis
is getting recognized as a valid route for (i) materials and valuable
products and petrochemicals recovery; (ii) waste recycling; and (iii)
elemental characterization. Pyrolysis is also receiving renewed
attention for its operational, economical and environmental
advantages. In this study, samples of polyethylene terephthalate
(PET) and polystyrene (PS) were pyrolysed in a microthermobalance
reactor (using a thermogravimetric-TGA setup). Both
polymers were prepared and conditioned prior to experimentation.
The main objective was to determine the kinetic parameters of the
depolymerization reactions that occur within the thermal degradation
process. Overall kinetic rate constants (ko) and activation energies
(Eo) were determined using the general kinetics theory (GKT)
method previously used by a number of authors. Fitted correlations
were found and validated using the GKT, errors were within ± 5%.
This study represents a fundamental step to pave the way towards the
development of scaling relationship for the investigation of larger
scale reactors relevant to industry.
Abstract: Batch fermentation of 5, 10 and 25 g/L biodiesel
derived crude glycerol was carried out at 30, 37 and 450C by
Clostridium pasteurianum cells immobilized on silica. Maximum
yield of 1,3-propanediol (PDO) (0.60 mol/mol), and ethanol (0.26
mol/mol) were obtained from 10 g/L crude glycerol at 30 and 370C
respectively. Maximum yield of butanol (0.28 mol/mol substrate
added) was obtained at 370C with 25 g/L substrate. None of the three
products were detected at 45oC even after 10 days of fermentation.
Only traces of ethanol (0.01 mol/mol) were detected at 450C with 5
g/L substrate. The results obtained for 25 g/L substrate utilization
were fitted in first order rate equation to obtain the values of rate
constant at three different temperatures for bioconversion of glycerol.
First order rate constants for bioconversion of glycerol at 30, 37 and
45oC were found to be 0.198, 0.294 and 0.029/day respectively.
Activation energy (Ea) for crude glycerol bioconversion was
calculated to be 57.62 kcal/mol.
Abstract: In the present study, a procedure was developed to
determine the optimum reaction rate constants in generalized
Arrhenius form and optimized through the Nelder-Mead method. For
this purpose, a comprehensive mathematical model of a fixed bed
reactor for dehydrogenation of heavy paraffins over Pt–Sn/Al2O3
catalyst was developed. Utilizing appropriate kinetic rate expressions
for the main dehydrogenation reaction as well as side reactions and
catalyst deactivation, a detailed model for the radial flow reactor was
obtained. The reactor model composed of a set of partial differential
equations (PDE), ordinary differential equations (ODE) as well as
algebraic equations all of which were solved numerically to
determine variations in components- concentrations in term of mole
percents as a function of time and reactor radius. It was demonstrated
that most significant variations observed at the entrance of the bed
and the initial olefin production obtained was rather high. The
aforementioned method utilized a direct-search optimization
algorithm along with the numerical solution of the governing
differential equations. The usefulness and validity of the method was
demonstrated by comparing the predicted values of the kinetic
constants using the proposed method with a series of experimental
values reported in the literature for different systems.
Abstract: The bromination of five selected pharmaceuticals
(metoprolol, naproxen, amoxicillin, hydrochlorotiazide and
phenacetin) in ultrapure water and in three water matrices (a
groundwater, a surface water from a public reservoir and a secondary
effluent from a WWTP) was investigated. The apparent rate
constants for the bromination reaction were determined as a function
of the pH, and the sequence obtained for the reaction rate was
amoxicillin > naproxen >> hydrochlorotiazide ≈ phenacetin ≈
metoprolol. The proposal of a kinetic mechanism, which specifies the
dissociation of bromine and each pharmaceutical according to their
pKa values and the pH allowed the determination of the intrinsic rate
constants for every elementary reaction. The influence of the main
operating conditions (pH, initial bromine dose, and the water matrix)
on the degradation of pharmaceuticals was established. In addition,
the presence of bromide in chlorination experiments was
investigated. The presence of bromide in wastewaters and drinking
waters in the range of 10 to several hundred μg L-1 accelerated
slightly the oxidation of the selected pharmaceuticals during chorine
disinfection.
Abstract: Potassium monopersulfate has been decomposed in aqueous solution in the presence of Co(II). The process has been simulated by means of a mechanism based on elementary reactions. Rate constants have been taken from literature reports or, alternatively, assimilated to analogous reactions occurring in Fenton's chemistry. Several operating conditions have been successfully applied.
Abstract: The equilibrium, thermodynamics and kinetics of the
biosorption of Cd (II) and Pb(II) by a Spore Forming Bacillus (MGL
75) were investigated at different experimental conditions. The
Langmuir and Freundlich, and Dubinin-Radushkevich (D-R)
equilibrium adsorption models were applied to describe the
biosorption of the metal ions by MGL 75 biomass. The Langmuir
model fitted the equilibrium data better than the other models.
Maximum adsorption capacities q max for lead (II) and cadmium (II)
were found equal to 158.73mg/g and 91.74 mg/g by Langmuir model.
The values of the mean free energy determined with the D-R equation
showed that adsorption process is a physiosorption process. The
thermodynamic parameters Gibbs free energy (ΔG°), enthalpy (ΔH°),
and entropy (ΔS°) changes were also calculated, and the values
indicated that the biosorption process was exothermic and
spontaneous. Experiment data were also used to study biosorption
kinetics using pseudo-first-order and pseudo-second-order kinetic
models. Kinetic parameters, rate constants, equilibrium sorption
capacities and related correlation coefficients were calculated and
discussed. The results showed that the biosorption processes of both
metal ions followed well pseudo-second-order kinetics.