Kinetic study of p-nitrophenol photodegradation with modified TiO2 xerogels

in Chemical Engineering Journal (2012), 191

TiO2 xerogels were sensitized in one step by the in situ introduction of nickel (II) tetra(4-carboxyphenyl)porphyrin (TCPPNi) into the TiO2 matrix during sol–gel synthesis. Crystalline photoactive phase ... [more ▼]

TiO2 xerogels were sensitized in one step by the in situ introduction of nickel (II) tetra(4-carboxyphenyl)porphyrin (TCPPNi) into the TiO2 matrix during sol–gel synthesis. Crystalline photoactive phase TiO2-anatase was obtained without high thermal treatments and was determined by X-ray diffraction. The presence of TCPPNi in TiO2 xerogels was established by DR-UV/Vis and FT-IR spectroscopy. The introduction of porphyrin led to a diminution of the specific surface area of TiO2 xerogels, and this diminution was analyzed by nitrogen adsorption–desorption. The particle size was estimated by SEM. The xerogel surface charge state, which influences the interactions between pollutant and TiO2, was determined by measurement of the point of zero charge. The photoactivity of xerogels was evaluated for p-nitrophenol degradation in aqueous medium at 20 ◦C. Results showed that porphyrin doped TiO2 degraded more than 40% of the p-nitrophenol whereas non doped TiO2 xerogel degraded only 10% of the compound. Moreover, porphyrin was found to improve the photoactivity of TiO2 xerogels in a similar way to UV-A pretreatment. A kinetic study of p-nitrophenol degradation was then performed. Results showed that one type of active site corresponding to the hole of electron–hole pairs was created at the TiO2 surface by light and that the rate determining step was the reaction between the adsorbed p-nitrophenol molecule and the adsorbed OH• radical. The apparent activation energy was found to be equal to 12 kJ mol−1. [less ▲]

Large-scale synthesis of multi-walled carbon nanotubes in a continuous inclined mobile-bed rotating reactor by the catalytic chemical vapour deposition process using methane as carbon source

in Chemical Engineering Journal (2012)

Multi-walled carbon nanotubes (CNTs) were produced in a continuous inclined mobile-bed rotating reactor by the catalytic chemical vapour deposition of methane on a bimetallic Ni-Mo/MgO catalyst whose ... [more ▼]

Multi-walled carbon nanotubes (CNTs) were produced in a continuous inclined mobile-bed rotating reactor by the catalytic chemical vapour deposition of methane on a bimetallic Ni-Mo/MgO catalyst whose activity remains constant in the course of time. Measurements performed on the continuous reactor were validated to ensure that the installation worked correctly and that measurements were precise enough. The performance of the reactor was simulated using a model based on the chemical reactor engineering approach. Hypotheses of the model were verified, and a kinetic study was performed to obtain a kinetic rate expression and to determine the catalytic activity as a function of time. The purity level of produced CNTs depends on the desired properties of the product, so the operating conditions are linked to the purity level that is required. A minimal purity level corresponds to high carbon production, and a maximal purity level corresponds to high specific productivity. It was shown that operating conditions had to be fixed to reach a given specific productivity or a given carbon production, and the optimized operating conditions leading to those two opposite purity level objectives were established. [less ▲]

Influence of carbon xerogel textural properties on the dynamic adsorption of methyl iodide

in Chemical Engineering Journal (2011), 173(1), 19-28

X-ray microtomography coupled to image analysis has been used to study the influence of the adsorbent pore texture and the experimental conditions on the dynamic adsorption of methyl iodide in packed ... [more ▼]

X-ray microtomography coupled to image analysis has been used to study the influence of the adsorbent pore texture and the experimental conditions on the dynamic adsorption of methyl iodide in packed filters. By applying this imaging technique the internal axial adsorption profiles for increasing exposure times to the gas stream are analysed. This experimental technique establishes a new technology to study in situ the dynamic adsorption of volatile compounds. Resorcinol-formaldehyde based carbon xerogels have been used as adsorbents, as their pore texture can be tuned by changing the synthesis conditions. The textural characteristics of the adsorbents (surface areas and pore volumes) have been assessed by using nitrogen and carbon dioxide adsorption as well as mercury porosimetry. The methyl iodide dynamic adsorption results show that, for the same gas flow rate and CH3I inlet concentration, the adsorbed amount is highly dependent on large pore volumes. Thus, samples with almost the same micropore volumes (adsorption volumes) have different methyl iodide adsorption capacities, which are related to, the above mentioned, large pores. The influence of both the gas carrier flow rate and the methyl iodide inlet concentration on the adsorption can be explained using the so-called linear driving force model. This approach takes into account the fact that internal transport limitations are directly related to the pore texture. Moreover, the simulation of the dynamic adsorption process has allowed relating the simulated axial concentration profiles to the experimental X-ray microtomography data. [less ▲]

Motion of carbon nanotubes in a rotating drum: The dynamic angle of repose and a bed behavior diagram

in Chemical Engineering Journal (2009), 146(1), 143-147

The granular flow behavior of carbon nanotubes produced by the CCVD method in a laboratory continuous inclined rotary reactor and of a catalyst was experimentally studied using a rotating drum. The ... [more ▼]

The granular flow behavior of carbon nanotubes produced by the CCVD method in a laboratory continuous inclined rotary reactor and of a catalyst was experimentally studied using a rotating drum. The dynamic angle of repose of the bulk solid and the standard variation of the solid bed surface were determined as a function of rotational speed of the rotating drum and for several filling percentages of the drum. Whatever the carbon nanotube production conditions, the dynamic angle of repose and the standard variation of the solid bed depended only on the filling percentage of the drum. Results were very interesting for practical application to carbon nanotube production in an industrial continuous inclined rotary reactor, because the granular flow behavior was the same during the reaction throughout the length of the reactor and depended only on the reactor filling. A bed behavior diagram based on the drum rotational speed and on the drum filling percentage was also constructed experimentally. The flow behavior of the solid during carbon nanotube production was on the boundary between the slumping and the rolling modes, leading to a good mixing of gas and solid during the reaction and to an improvement of the mass and heat transfer in the bed. (c) 2008 Elsevier B.V. All rights reserved. [less ▲]

Pd-Ag/SiO2 xerogel catalyst forming by impregnation on alumina foams

in Chemical Engineering Journal (2006), 117(1), 13-22

A Pd-Ag/SiO2 xerogel catalyst prepared in one step by sol-gel process has been entrapped in cylindrical porous alumina foams of three different pore sizes in order to shape the catalyst under the ... [more ▼]

A Pd-Ag/SiO2 xerogel catalyst prepared in one step by sol-gel process has been entrapped in cylindrical porous alumina foams of three different pore sizes in order to shape the catalyst under the appropriate form with suitable mechanical resistance to be used in an industrial fixed bed reactor. After drying, calcination and reduction, the Pd-Ag/SiO2 xerogel catalyst pellets are immobilized inside the open porosity of the alumina foam. The localization of the xerogel catalyst in the alumina foams has been studied by X-ray tomography. The three-dimensional porous structure was reconstructed from the consecutive cross-sections obtained by this technique. This method shows that the Pd-Ag/SiO2 xerogel catalyst is uniformly dispersed inside the porosity of the alumina foams. Activity and selectivity of Pd-Ag/SiO2 xerogel catalyst reference or catalyst entrapped in alumina foams have been studied for selective hydrodechlorination of 1,2-dichloroethane into ethylene. The specific reaction rate obtained with catalyst entrapped in alumina foams is smaller than the one obtained from corresponding catalyst powders. The catalytic activity decrease observed for Pd-Ag/SiO2 xerogel catalyst entrapped in porous alumina foams most probably arises from diffusional limitations inside the porous texture of the alumina foams. (c) 2005 Elsevier B.V. All rights reserved. [less ▲]

Structured mixing model for stirred bioreactors : an extension to the stochastic approach

in Chemical Engineering Journal (2005)

Axial dispersion processes in liquid trickle flow through packed bed

in Chemical Engineering Journal (1982), 25