Abstract: Catalytic oxidation of benzene assisted by ozone, on alumina, silica, and boehmite-supported Ni/Pd catalysts was investigated at 353 K to assess the influence of the support on the reaction. Three bimetallic Ni/Pd nanosized samples with loading 4.7% of Ni and 0.17% of Pd supported on SiO2, AlOOH and Al2O3 were synthesized by the extractive-pyrolytic method. The phase composition was characterized by means of XRD and the surface area and pore size were estimated using Brunauer–Emmett–Teller (BET) and Barrett–Joyner–Halenda (BJH) methods. At the beginning of the reaction, catalysts were significantly deactivated due to the accumulation of intermediates on the catalyst surface and after 60 minutes it turned stable. Ni/Pd/AlOOH catalyst showed the highest steady-state activity in comparison with the Ni/Pd/SiO2 and Ni/Pd/Al2O3 catalysts. Their activity depends on the ozone decomposition potential of the catalysts because of generating oxidizing active species. The sample with the highest ozone decomposition ability which correlated to the surface area of the support oxidizes benzene to the highest extent.
Abstract: The combination of world population and the third industrial revolution led to high demand for fuels. On the other hand, the decrease of global fossil 8fuels deposits and the environmental air pollution caused by these fuels has compounded the challenges the world faces due to its need for energy. Therefore, new forms of environmentally friendly and renewable fuels such as biodiesel are needed. The primary analytical techniques for methanolysis yield monitoring have been chromatography and spectroscopy, these methods have been proven reliable but are more demanding, costly and do not provide real-time monitoring. In this work, the in situ monitoring of biodiesel from sunflower oil using FTIR (Fourier Transform Infrared) has been studied; the study was performed using EasyMax Mettler Toledo reactor equipped with a DiComp (Diamond) probe. The quantitative monitoring of methanolysis was performed by building a quantitative model with multivariate calibration using iC Quant module from iC IR 7.0 software. 15 samples of known concentrations were used for the modelling which were taken in duplicate for model calibration and cross-validation, data were pre-processed using mean centering and variance scale, spectrum math square root and solvent subtraction. These pre-processing methods improved the performance indexes from 7.98 to 0.0096, 11.2 to 3.41, 6.32 to 2.72, 0.9416 to 0.9999, RMSEC, RMSECV, RMSEP and R2Cum, respectively. The R2 value of 1 (training), 0.9918 (test), 0.9946 (cross-validation) indicated the fitness of the model built. The model was tested against univariate model; small discrepancies were observed at low concentration due to unmodelled intermediates but were quite close at concentrations above 18%. The software eliminated the complexity of the Partial Least Square (PLS) chemometrics. It was concluded that the model obtained could be used to monitor methanol of sunflower oil at industrial and lab scale.
Abstract: Spent catalysts are considered as hazardous residues of major concern, mainly due to the simultaneous presence of several metals in elevated concentrations. Although hydrometallurgical, pyrometallurgical and chelating agent methods are available to remove and recover some metals contained in spent catalysts; these procedures generate potentially hazardous wastes and the emission of harmful gases. Thus, biotechnological treatments are currently gaining importance to avoid the negative impacts of chemical technologies. To this end, diverse microorganisms have been used to assess the removal of metals from spent catalysts, comprising bacteria, archaea and fungi, whose resistance and metal uptake capabilities differ depending on the microorganism tested. Acidophilic sulfur oxidizing bacteria have been used to investigate the biotreatment and extraction of valuable metals from spent catalysts, namely Acidithiobacillus thiooxidans and Acidithiobacillus ferroxidans, as they present the ability to produce leaching agents such as sulfuric acid and sulfur oxidation intermediates. In the present work, the ability of A. thiooxidans DSM 26636 for the bioleaching of metals contained in five different spent catalysts was assessed by growing the culture in modified Starkey mineral medium (with elemental sulfur at 1%, w/v), and 1% (w/v) pulp density of each residue for up to 21 days at 30 °C and 150 rpm. Sulfur-oxidizing activity was periodically evaluated by determining sulfate concentration in the supernatants according to the NMX-k-436-1977 method. The production of sulfuric acid was assessed in the supernatants as well, by a titration procedure using NaOH 0.5 M with bromothymol blue as acid-base indicator, and by measuring pH using a digital potentiometer. On the other hand, Inductively Coupled Plasma - Optical Emission Spectrometry was used to analyze metal removal from the five different spent catalysts by A. thiooxidans DSM 26636. Results obtained show that, as could be expected, sulfuric acid production is directly related to the diminish of pH, and also to highest metal removal efficiencies. It was observed that Al and Fe are recurrently removed from refinery spent catalysts regardless of their origin and previous usage, although these removals may vary from 9.5 ± 2.2 to 439 ± 3.9 mg/kg for Al, and from 7.13 ± 0.31 to 368.4 ± 47.8 mg/kg for Fe, depending on the spent catalyst proven. Besides, bioleaching of metals like Mg, Ni, and Si was also obtained from automotive spent catalysts, which removals were of up to 66 ± 2.2, 6.2±0.07, and 100±2.4, respectively. Hence, the data presented here exhibit the potential of A. thiooxidans DSM 26636 for the simultaneous bioleaching of metals contained in spent catalysts from diverse provenance.
Abstract: SSZ-13 materials with different Si/Al ratio were prepared by varying the composition of aluminosilicate precursor solutions upon hydrothermal treatment at 150 °C. The Si/Al ratio of the initial system was systematically changed from 12.5 to infinity in order to study the limits of Al composition in precursor solutions for constructing CHA structure. The intermediates and final products were investigated by complementary techniques such as XRD, HRTEM, FESEM, and chemical analysis. NH3-TPD was used to study the Brønsted acidity of SSZ-13 samples with different Si/Al ratios. The effect of the Si/Al ratio on the precursor species, ultimate crystal size, morphology and yield was investigated. The results revealed that Al species determine the nucleation rate and the number of nuclei, which is tied to the morphology and yield of SSZ-13. The size of SSZ-13 increased and the yield decreased as the Si/Al ratio was improved. Varying Si/Al ratio of the initial system is a facile, commercially viable method of tailoring SSZ-13 crystal size and morphology. Furthermore, SSZ-13 materials with different Si/Al ratio were tested as catalysts for the methanol to olefins (MTO) reaction at 350 °C. SSZ-13 with the Si/Al ratio of 35 shows the best MTO catalytic performance.
Abstract: In Dynamic Data Envelopment Analysis (DDEA), which is a subfield of Data Envelopment Analysis (DEA), the productivity of Decision Making Units (DMUs) is considered in relation to time. In this case, as it is accepted by the most of the researchers, there are outputs, which are produced by a DMU to be used as inputs in a future time. Those outputs are known as intermediates. The common models, in DDEA, do not take into account the shape of the distribution of those inputs, outputs or intermediates data, assuming that the distribution of the virtual value of them does not deviate from linearity. This weakness causes the limitation of the accuracy of the analytical power of the traditional DDEA models. In this paper, the authors, using the concept of piecewise linear inputs and outputs, propose an extended DDEA model. The proposed model increases the flexibility of the traditional DDEA models and improves the measurement of the dynamic performance of DMUs.
Abstract: The performance of organophosphorus extractants Cyanex 272 and D2EHPA on the purification of concentrate nickel sulfate solutions was evaluated. Batch scale tests were carried out at pH range of 2 to 7 using a laboratory solution simulating concentrate nickel liquors as those typically obtained when sulfate intermediates from nickel laterite are re-leached and treated for the selective removal of cobalt, zinc, manganese and copper with Cyanex 272 ([Ca] = 0.57 g/L, [Mg] = 3.2 g/L, and [Ni] = 88 g/L). The increase on the concentration of D2EHPA favored the calcium extraction. The extraction of magnesium is dependent on the pH and of ratio of extractants D2EHPA and Cyanex 272 in the organic phase. The composition of the investigated organic phase did not affect nickel extraction. The number of stages is dependent on the magnesium extraction. The most favorable operating condition to selectively remove calcium and magnesium was determined.
Abstract: This paper discusses the importance of having a good initial characterization of soil samples when thermal desorption has to be applied to polluted soils for the removal of contaminants. Particular attention has to be devoted on the desorption kinetics of the samples to identify the gases evolved during the heating, and contaminant degradation pathways. In this study, two samples coming from different points of the same contaminated site were considered. The samples are much different from each other. Moreover, the presence of high initial quantity of heavy hydrocarbons strongly affected the performance of thermal desorption, resulting in formation of dangerous intermediates. Analytical techniques such TGA (Thermogravimetric Analysis), DSC (Differential Scanning Calorimetry) and GC-MS (Gas Chromatography-Mass) provided a good support to give correct indication for field application.
Abstract: This first-attempt study revealed that decolorized
intermediates of azo dyes could act as redox mediators to assist
wastewater (WW) decolorization due to enhancement of
electron-transport phenomena. Electrochemical impedance spectra
indicated that hydroxyl and amino-substituent(s) were functional
group(s) as redox-mediator(s). As azo dyes are usually multiple
benzene-rings structured, their derived decolorized intermediates are
likely to play roles of electron shuttles due to lower barrier of energy
gap for electron shuttling. According to cyclic voltammetric profiles,
redox mediating characteristics of decolorized intermediates of azo
dyes (e.g., RBu171, RR198, RR141, RBk5) were clearly disclosed.
With supplementation of biodecolorized metabolites of RR141 and
198, decolorization performance of could be evidently augmented.
This study also suggested the optimal modes of microbial fuel cell
(MFC)-assisted WW decolorization would be plug-flow or batch
mode of operation with no mix. Single chamber-MFCs would be more
favourable than double chamber MFCs due to non-mixing contacting
reactor scheme for operation.
Abstract: Low Temperature Matrix Isolation - Electron
Paramagnetic Resonance (LTMI-EPR) Spectroscopy was utilized to
identify the species of iron oxide nanoparticles generated during the
oxidative pyrolysis of 1-methylnaphthalene (1-MN). The otherwise
gas-phase reactions of 1--MN were impacted by a polypropylenimine
tetra-hexacontaamine dendrimer complexed with iron (III) nitrate
nonahydrate diluted in air under atmospheric conditions. The EPR
fine structure of Fe (III)2O3 nanoparticles clusters, characterized by gfactors
of 2.00, 2.28, 3.76 and 4.37 were detected on a cold finger
maintained at 77 K after accumulation over a multitude of
experiments. Additionally, a high valence Fe (IV) paramagnetic
intermediate and superoxide anion-radicals, O2•- adsorbed on
nanoparticle surfaces in the form of Fe (IV) --- O2•- were detected
from the quenching area of Zone 1 in the gas-phase.
Abstract: In the present study, presence of endosulfan, imidacloprid, carbendazim, in the soil /vegetables/cereals and water samples was observed in agriculture fields of Uttarakhand. In view of biodegradation of these pesticides, 9 bacterial isolates were recovered from the soil samples of the fields which tolerated endosulfan, imidacloprid, carbendazim from 100 to 200 µg/ml. Three bacterial consortia used for in vitro bioremediation experiments were consisted of 3 bacterial isolates for carbendazim, imidacloprid and endosulfan, respectively. Maximum degradation (87 and 83%) of α and β endosulfan respectively was observed in soil slurry by consortium. Degradation of Imidacloprid and carbendazim under similar conditions was 88.4 and 77.5% respectively. FT-IR analysis of biodegraded samples of pesticides in liquid media showed stretching of various bonds. GC-MS of biodegraded endosulfan sample in soil slurry showed the presence of nontoxic intermediates. A pot trial with Bacterial treatments lowered down the uptake of pesticides in onion plants.
Abstract: In this study, photocatalytic degradation of phenol by
titanium dioxide (TiO2) in aqueous solution was evaluated. The UV
energy of solar light was utilized by compound parabolic collectors
(CPCs) technology. The effect of irradiation time, initial pH, and
dosage of TiO2 were investigated. Aromatic intermediates (catechol,
benzoquinone, and hydroquinone) were quantified during the reaction
to study the pathways of the oxidation process. 94.5% degradation
efficiency of phenol was achieved after 150 minutes of irradiation
when the initial concentration was 100 mg/L. The dosage of TiO2
significantly affected the degradation efficiency of phenol. The
observed optimum pH for the reaction was 5.2. Phenol photocatalytic
degradation fitted to the pseudo-first order kinetic according to
Langmuir–Hinshelwood model.
Abstract: Chemical vapor deposition method was used to
produce carbon nanotubes on an iron based catalyst from acetylene.
Gas-phase samples collected from the different positions of the tubular reactor were analyzed by GC/MS. A variety of species ranging from hydrogen to naphthalene were observed and changes in their concentrations were plotted against the reactor position. Briefly benzene, toluene, styrene, indene and naphthalene were the main
higher molecular weight species and vinylacetylene and diacetylene were the important intermediates. Nanotube characterization was performed by scanning electron microscopy and transmission electron microscopy.
Abstract: Curing of paints by exposure to UV radiations is
emerging as one of the best film forming technique as an alternative
to traditional solvent borne oxidative and thermal curing coatings.
The composition and chemistry of UV curable coatings and role of
multifunctional and monofunctional monomers, oligomers, and
photoinitiators have been discussed. The limitations imposed by
thermodynamic equilibrium and tendency for acrylic double bond
polymerizations during synthesis of multifunctional acrylates have
been presented. Aim of present investigation was thus to explore the
reaction variables associated with synthesis of multifunctional
acrylates. Zirconium oxychloride was evaluated as catalyst against
regular acid functional catalyst. The catalyzed synthesis of glyceryl
acrylate and neopentyl glycol acrylate was conducted by variation of
following reaction parameters: two different reactant molar ratios-
1:4 and 1:6; catalyst usage in % by moles on polyol- 2.5, 5.0 and 7.5
and two different reaction temperatures- 45 and 75 0C. The reaction
was monitored by determination of acid value and hydroxy value at
regular intervals, besides TLC, HPLC, and FTIR analysis of
intermediates and products. On the basis of determination of reaction
progress over 1-60 hrs, the esterification reaction was observed to
follow 2nd order kinetics with rate constant varying from 1*10-4 to
7*10-4. The thermal and catalytic components of second order rate
constant and energy of activation were also determined. Uses of
these kinetic and thermodynamic parameters in design of reactor for
manufacture of multifunctional acrylate ester have been presented.
The synthesized multifunctional acrylates were used to formulate and
apply UV curable clear coat followed by determination of curing
characteristics and mechanical properties of cured film. The overall
curing rates less than 05 min. were easily attained indicating
economical viability of radiation curable system due to faster
production schedules
Abstract: The photochemical and photo-Fenton oxidation of 1,3-dichloro-2-propanol was performed in a batch reactor, at room temperature, using UV radiation, H2O2 as oxidant, and Fenton-s reagent. The effect of the oxidative agent-s initial concentration was investigated as well as the effect of the initial concentration of Fe(II) by following the target compound degradation, the total organic carbon removal and the chloride ion production. Also, from the kinetic analysis conducted and proposed reaction scheme it was deduced that the addition of Fe(II) significantly increases the production and the further oxidation of the chlorinated intermediates.
Abstract: Excilamps are new UV sources with great potential
for application in wastewater treatment. In the present work, a XeBr
excilamp emitting radiation at 283 nm has been used for the
photodegradation of 4-chlorophenol within a range of concentrations
from 50 to 500 mg L-1. Total removal of 4-chlorophenol was
achieved for all concentrations assayed. The two main photoproduct
intermediates formed along the photodegradation process,
benzoquinone and hydroquinone, although not being completely
removed, remain at very low residual concentrations. Such
concentrations are insignificant compared to the 4-chlorophenol
initial ones and non-toxic. In order to simulate the process and scaleup,
a kinetic model has been developed and validated from the
experimental data.
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: The chemical degradation of dieldrin in ferric
sulfide and iron powder aqueous suspension was investigated
in laboratory batch type experiments. To identify the reaction
mechanism, reduced copper was used as reductant. More than
90% of dieldrin was degraded using both reaction systems after
29 days. Initial degradation rate of the pesticide using ferric
sulfide was superior to that using iron powder. The reaction
schemes were completely dissimilar even though the ferric ion
plays an important role in both reaction systems. In the case of
metallic iron powder, dieldrin undergoes partial dechlorination.
This reaction proceeded by reductive hydrodechlorination with
the generation of H+, which arise by oxidation of ferric iron.
This reductive reaction was accelerated by reductant but
mono-dechlorination intermediates were accumulated. On the
other hand, oxidative degradation was observed in the reaction
with ferric sulfide, and the stable chemical structure of dieldrin
was decomposed into water-soluble intermediates. These
reaction intermediates have no chemical structure of drin class.
This dehalogenation reaction assumes to occur via the adsorbed
hydroxyl radial generated on the surface of ferric sulfide.
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: 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: Crystallization has been used for the separation of
chloronitrobenzene or CNBs, which are isomeric substances (o-, mand
p-CNB) and important intermediates in chemical productions. Effects of feed composition on the crystallization of m- and p-CNB was first studied. The results conform to the binary phase diagram of
m- and p-CNB. After that, effects of FAU zeolites (NaX, CaX, BaX, NaY and CaY) above the eutectic composition (63.5 and 65.0 wt% m-CNB in the feed) was also investigated. The results showed that
the FAU zeolites significantly affected the precipitates, the
composition of which was shifted from being rich in m-CNB to rich
in p-CNB. Effects of the number of FAU zeolites on the precipitate composition was then studied. The results revealed that the
precipitates from the lower number of the zeolites had higher p-CNB purity than those from the higher number of zeolite.