Carine Julcour-Lebigue

• Ph.D. in Chemical Engineering
• Senior Researcher at Laboratoire de Génie Chimique, French National Centre for Scientific Research

This study’s aim is to fully characterize ferronickel slag from New Caledonia, considered a multiphase mineral containing amorphous material. The methodology consisted of combining chemical, mineral, and morphological characterization techniques, such as ICP-AES, TGA, Q-XRD, microscopy, spectroscopy, etc. The ferronickel slag consisted of 44 wt. %...

We report the investigation of a chalcopyrite leaching process that implements millimeter-sized glass beads that are stirred in the leach reactor to combine particle grinding, mechanical activation, and surface removal of reaction products. The paper focuses on demonstrating the impact of the so-called attrition-leaching phenomenon on the leaching...

The main obstacle to the aqueous carbonation of non-serpentinised magnesium silicates is the formation of surface passivation layers, which severely limits the reaction rate and thus the overall efficiency of the process. A technological solution to overcome this problem is to perform the carbonation process inside a stirred bead mill, which aims t...

The world is facing critical technological and environmental challenges in the production of basic materials in high demand, such as aluminium and silica, whose processes were developed long ago. New production routes, involving using alternative resources and innovative technological solutions, are needed to secure access to these base materials a...

Dynamic reactor operations will gain interest with the increase of intermittent electricity from renewable sources. Periodic operation of catalytic reactors can also be used for kinetic studies with better parameter estimation than steady‐state operation. This methodology is exemplified for the case of acetylene hydrogenation over Pd/α‐Al2O3 using...

Several homogeneous photo-based advanced oxidation processes-namely photolysis, photo-oxidation, and photo-Fenton oxidation—were investigated for the elimination of ibuprofen in water. The effects of several operating parameters, such as the lamp type (low or medium pressure mercury, xenon-arc), the concentration of hydrogen peroxide (0.5 to 7 time...

A kinetic model for sunflower oil hydrogenation on a palladium catalyst is proposed based on Horiuty-Polanyi type mechanism and considering either a dissociative or associative adsorption of hydrogen. The derived kinetic laws allow to explain the distinct dependency of saturation and isomerization reactions on hydrogen pressure. Kinetic parameters...

This work is part of the ongoing development of the attrition-leaching carbonation process, a single-step aqueous carbonation technology that integrates a stirred bead mill. The principle of the attrition-leaching carbonation process is to continuously refresh the surfaces of reactive particles so that leaching can proceed unimpeded, yielding enhan...

This paper is part of a multi-disciplinary research program on development and application of an integrated CO2 mineralization (ICM) framework for development of carbon mineralization as a CO2 mitigation solution. ICM is viewed as a three concentric layer system: technological, industrial integration, and decision-making. The search for viable ICM...

While activated sludge treatment is currently the preferred process for the removal of tributyl phosphate (TBP) at the mg.L⁻¹ level, it is well known that this recalcitrant molecule is incompletely degraded, stimulating research into alternative approaches, such as advanced oxidation. The aim of this study was to characterize the degradation mechan...

The viscosity of edible oils was measured before and after hydrogenation to assess a new model for predicting the viscosity of partially hydrogenated oils with given saturation degree and temperature. This contribution group model is based on a semi-predictive approach, and can be used to estimate viscosity changes due to hydrogenation. It was expe...

This work investigates the ultrasound propagation within a liquid-solid fluidized bed. The acoustic mapping of the reactor is achieved by means of a hydrophone. A spectral analysis is carried out on the measured signals to quantify the cavitation activity. The effects of several parameters on the spectral power distribution is appraised – including...

Mineralization is a CO2 utilization solution that can possibly meet all the CO2 mitigation criteria stated by the International Energy Agency, namely CO2 emissions reduction, economic self-sufficiency and scalability. Considered as a global niche markets solution, mineralization process development is particularly challenging, as its scope is terri...

Heterogeneous Fenton oxidation using Fe-zeolite catalyst (of ZSM5 type) was investigated for the removal of ibuprofen (20 mg/L) in water. In particular, the effects of catalyst concentration, oxidant dosage, temperature, solution pH, and water matrix on pollutant conversion and mineralization were evaluated. The activity of leached iron species in...

Efficient catalyst recovery and recycling is still a major challenge for the development of homogeneous catalysis. In the 80’s, the concept of biphasic catalysis, in which the catalyst is confined into a solvent immiscible with the products, has opened new perspectives for transition metal complex driven homogeneous catalysis, after the industrial...

The formation of passivation layers is the major obstacle to the development of direct aqueous mineral carbonation of magnesium silicates, one of the most promising routes for large-scale CO2 mitigation. This observation has led to considerable research efforts to prevent the formation of these layers and/or to exfoliate them continuously during th...

This work aimed at comparing different UV and H2O2 based advanced oxidation processes (AOPs) −photolysis, UV/H2O2, and photo-Fenton reaction- for the degradation of 2,4-dichlorophenoxyacetic acid (2,4-D), a common ingredient of phytosanitary products. The influence of oxidant dose (H2O2), catalyst type and concentration, pollutant concentration, wa...

Pesticide pollution of surface water and groundwater has been recognized as a major problem in many countries because of the persistence of pollutants in aquatic environments and the consequent potential adverse health effects. Advanced oxidation processes (AOPs) constitute important, promising and efficient methods developed to remove persistent o...

Intensive use of chlorinated pesticides from the 1960s to the 1990s has resulted in a diffuse contamination of soils and surface waters in the banana-producing areas of the French West Indies. The purpose of this research was, for the first time, to examine the degradation of two of these persistent pollutants – chlordecone (CLD) and beta-hexachlor...

Two-phase monolith-type reactors allow intensified heat and mass transfer rates, but often suffer from fluid maldistribution and undesired flow regimes in channels. A cold-flow monolith reactor (0.1 m diameter, 84 channels) is used here to assess liquid distribution and flow regimes at various air and water velocities: resistive probes give an insi...

Oxidative regeneration of activated carbon exhausted with phenolic compounds is still a challenging issue due to the frequent porosity loss. Addition of low H2O2 amount is investigated as a way to promote catalytic wet air oxidation (CWAO) of adsorbed pollutants and thereby to recover absorbent properties. Commercial activated carbon and transition...

The 15th International Conference on QiR - Quality in Research 2017:742-751 http://qir.eng.ui.ac.id/qir-proceedings/

This study aimed at developing an innovative catalytic reactor inspired from monolith technology and equipped with in situ heat removal system. To illustrate the approach, the total hydrogenation of a bio-sourced olefin, alpha-pinene, was chosen as a model reaction. Preliminary thermal calculations proved the proposed reactor-heat exchanger configu...

Two sonochemical processes were compared for the removal of ibuprofen in different water matrixes (distilled water and effluent from wastewater treatment plant). The effect of various operating parameters, such as pH (2.6–8.0), ultrasound power density (25–100 W/L), sonication frequency (12–862 kHz), addition of radical promoters (H2O2 and Fenton's...

This work focuses on the regeneration of a zeolite catalyst from industry deactivated by fouling with coke. To replace high temperature combustion, a common and energy intensive process, an oxidation process under milder conditions (50 °C–200 °C) has been investigated using ozone. Coked zeolite has been oxidized by an ozone stream in a fixed bed re...

Biphasic homogeneous protocols are attractive for catalyzed transformations in industry, especially when conducted with water as the catalyst phase as exemplified by the large-scale Rhône-Poulenc/Ruhrchemie hydroformylation process, but can only be applied when the substrate is sufficiently soluble in the aqueous phase to sustain sufficiently fast...

Keywords Regeneration; Coke; Ozone; Heterogeneous catalyst; Zeolite; Oxidation; Process optimization

Approximately 80% of industrial processes currently use heterogeneous catalysts because of their various advantages. However, their major drawback is deactivation which can occur over variable time scales (from seconds to several years). This phenomenon can be generated by several mechanisms [1]: poisoning (chemisorption of impurities or by-product...

Amphiphilic phosphine-functionalized nanogel particles were synthesized by aqueous polymerization-induced self-assembly insuring a well-defined architecture as well as a narrow size distribution (average diameter of ca. 90 nm in water). They were successfully applied as ligands for the biphasic hydroformylation of 1-octene catalyzed by rhodium, yie...

Paracetamol is commonly found in wastewaters, as a consequence of its high consumption and incomplete elimination by conventional treatments. Homogenous (photo-)Fenton oxidation has proved efficient for its remediation, but it suffers from uneasy dissolved iron recovery. Therefore this work examines the performance and stability of an iron containi...

Environmental hazards are a consequence of the massive use of synthetic chemicals that are prevalent in nearly every aspect of modern life. The outburst of the so-called "emerging pollutants" (pharmaceuticals and pesticides among others) generates an additional problem due to the scarce available information on their impact on the environment or th...

A strategy for the scale-up of a monolith reactor dedicated to gas-liquid catalytic reactions is worked out; focus is made on the crucial step of gas-liquid mass transfer modelling via a steady-state numerical study based on a single channel and single unit cell representation, using a frame moving with the bubble and solving the liquid phase only....

The effect of hydrostatic pressure on sludge disintegration was studied for the first time using pressurized nitrogen in different operating conditions: sludge types, specific energy input ES, power input PUS, probe size, temperature T, and frequency FS. Optimum pressures (> 1 bar) were found as a function of acoustic intensity due to an increase i...

Impregnation of a commercial activated carbon (AC) with transition metals was investigated to extend its reuse as phenol adsorbent after regeneration by catalytic wet air oxidation (CWAO). Iron and copper catalysts were prepared with varied metal dispersions and oxidation states by using different heat treatments. The main feature of the iron catal...

Ultrasonication (US), which creates hydro-mechanical shear forces in cavitation, is an advanced technology in sludge pretreatment. However, there are many factors affecting the efficacy of cavitation and ultrasonication disintegration of sludge as a consequence. The objective of this work is to present an extensive review of evaluation approaches o...

Approximately 80% of industrial processes currently use heterogeneous catalysts because of their various advantages. Indeed, reuse of these solid catalysts is common since they can be easily separated from a reaction medium, e.g. by simple filtration. They are used in various application fields such as air/wastewater treatment, petrochemicals and f...

Controlled radical polymerization has recently been used to develop polymers engineered for applications as catalytic nanoreactors. In this contribution, we present the joint development, in our laboratories, of core-cross-linked micelles (CCM) for application under aqueous biphasic conditions through the micellar approach, using triphenylphosphine...

High catalytic activity (turnover frequencies up to 700 h−1) was achieved using new triphenylphosphine-functionalized core cross-linked micelles, TPP@CCM, as nanoreactors and [Rh(acac)(CO)2] as catalyst precursor for the aqueous biphasic hydroformylation of 1-octene. While the hydrophobic core of the polymer offers an adequate environment for the c...

Tóm tắt This work aimed at investigating the effect of audible frequency ( FS = 12 kHz) on sludge pretreatment by sonication ( US) under pressure for the first time. The main US parameters (power - PUS, intensity - IUS) were also looked into. The higher PUS, the higher sludge disintegration ( DDCOD) was achieved due to the increase in cavitation i...

Tóm tắt Sludge particle size reduction (PSR) via pretreatment stage has been believed to accelerate the hydrolysis of sludge anaerobic digestion and enhance the degradation of organic matters. It is therefore one of important factors used to describe the effect of pretreatment on sludge. This work aimed at investigating the evolution of PSR under...

Core-cross-linked micelles (CCM) functionalized at the core with covalently linked bis(p-methoxyphenyl) phenylphosphine (BMOPPP) ligands have been synthesized by a three-step one-pot radical polymerization in emulsion, using the polymerization-induced self-assembly (PISA) strategy and reversible addition-fragmentation chain transfer (RAFT) as the c...

The work investigates the effect of iron or copper doping on Activated Carbon activity in standard and peroxide-promoted CWAO, as well as on its lifetime as adsorbent/catalyst in a sequential ADsorption/Oxidation process. Catalysts were prepared and tested during successive ADOX cycles. Analyses indicated negligible leaching (<2%) and preservation...

Water-borne phosphine-functionalized core-cross-linked micelles (CCM) consisting of a hydrophobic core and a hydrophilic shell were obtained as stable latexes by reversible addition-fragmentation chain transfer (RAFT) in water in a one-pot, three-step process. Initial homogeneous aqueous-phase copolymerization of methacrylic acid (MAA) and poly(eth...

This work aims at investigating for the first time the key sonication (US) parameters: power density (DUS), intensity (IUS), and frequency (FS) - down to audible range, under varied hydrostatic pressure (Ph) and low temperature isothermal conditions (to avoid any thermal effect). The selected application was activated sludge disintegration, a major...

This work aimed at investigating the importance of ultrasound (US) power (PUS) vs. probe size in terms of US intensity (IUS) effect on sludge US pretreatment, assessed mainly based on the degree of sludge disintegration (DDCOD). All experiments were conducted in isothermal condition (low temperature) to deeply understand mechanical effect of US. Fo...

This article presents the main outputs from the multidisciplinary Carmex project (2009–2012), which was concerned with the possibility of applying ex situ mineral carbonation concepts to mafic/ultramafic mining wastes. Focus points of the project included (i) matching significant and accessible mining wastes to large CO2 emitters through a dedicate...

100 mg L-1 paracetamol aqueous solutions were treated by heterogeneous Fenton oxidation at acidic pH (2.6). Three types of iron oxides - nano- and submicro-structured magnetite, nanostructured maghemite - were tested as catalysts for that purpose. For each system, the paracetamol conversion and mineralization yield (Total Organic Carbon removal) we...

This work aimed at understanding the combined effect of sludge pH, temperature, and external pressure on the efficiency of sewage sludge ultrasound (US) pretreatment. Based on the evolution of both the degree of sludge disintegration (DDCOD) and pH, application of 40 mgNaOH/gTS during 30 min was selected for chemical pretreatment. Mechanical and th...

A series of well defined polystyrene supported tertiary phosphine ligands were prepared by copper catalyzed atom transfer radical polymerization (ATRP), involving direct copolymerization of styrene and 4-styryldiphenylphosphine (SDPP). Copolymerization of the two monomers at different molar ratios showed a decreasing level of control as the SDPP mo...

This article presents the main results of the Carmex project (2009-2012), whose purpose was to review the feasibility of ex-situ mineral carbonation in terms of resource availability, performance of the aqueous mineral carbonation process and life cycle analysis criteria. This collaborative project looked at a wide range of generic issues about thi...

Well defined star copolymers have been prepared by copper-catalyzed atom transfer radical copolymerization of styrene and styryldiphenylphosphine starting from a modified Boltorn™ H30 multifunctional initiator. These polymers and an analogue obtained by debromination of the arm ends with nBu3SnH have been used in combination with [Rh(acac)(CO)2] fo...

A new sequential process, AD–OX, for (post)treatment of water polluted by poorly biodegradable organic compounds has been investigated. It is based on hybridizing classical adsorption on a fixed bed of activated carbon (AC) followed by batch wet catalytic oxidation at higher temperature and pressure on the same bed of AC, which is then regenerated...

Direct aqueous mineral carbonation using organic anions has been presented by many as a promising strategy for mineral carbonation, on the basis that additives such as oxalate increase the rate and extent of dissolution of magnesium silicates several folds. Through geochemical modelling and detailed solid characterisation, this paper discusses and...

The concern about the fate of pharmaceutical products has raised owing to the increasing contamination of rivers, lakes and groundwater. The aim of this paper is to evaluate two different processes for paracetamol removal. The catalytic wet air oxidation (CWAO) of paracetamol on activated carbon was investigated both as a water treatment technique...

The competitive adsorption of phenol and para-hydroxybenzoic acid (4HBA) has been investigated on activated carbon (AC) for a wide range of concentrations under unbuffered conditions. The results show a preferential adsorption of 4HBA which can be explained by the lower solubility of 4HBA and the electrostatic interactions between the AC and the io...

Amongst possible mineral carbonation strategies, direct aqueous mineral carbonation using organic salts is perhaps the most promising one. By going to and from between geochemical modelling and experimental results, this paper reviews key findings and conclusions to date about this process. With the magnesium silicate – oxalate system, the paper ma...

In this work we present the first preparation of (co)polymer supported tertiary phosphine ligands by atom transfer radical polymerization (ATRP), foreseeing catalysts recovery and recycling. Styrildiphenylphosphine (SDPP) has been homo- and copolymerized with styrene in different ratios. The higher the SDPP percentage, the less controlled the polym...

Biphasic hydroformylation of 1-octene was performed using rhodium sulfoxantphos catalyst dissolved in [BuPy][BF4] ionic liquid. Preliminary experiments proved this system to retain the catalytic complex within the ionic liquid phase and to maintain a high selectivity towards the linear aldehyde (n:iso ratio of 30) over several cycles. Process param...

This paper describes a preliminary evaluation of the performance of carbonaceous materials prepared from sewage sludges (SBCMs) in a hybrid water treatment process based on adsorption and catalytic wet air oxidation; phenol was used as the model pollutant. Three different sewage sludges were treated by either carbonisation or steam activation, and...

Catalytic wet air oxidation (CWAO) of phenolic compounds over three activated carbons (ACs) has been investigated in a semibatch autoclave to better understand the influence of AC properties on the efficiency and stability of CWAO. Phenol, 4-nitrophenol, 4-chlorophenol, and 4-hydroxybenzoic acid, as well as synthetic mixtures comprising two to four...

A chemical reaction engineering approach is reported to investigate the biphasic hydroformylation of 1-octene using [bmim][PF6] ionic liquid. It is based both on a process parameter investigation (temperature, concentrations, and pressures) and a thermodynamic study of the reaction medium (gas−liquid and liquid−liquid equilibria). Initial rate data...

This work aims to study the adsorption of phenol on activated carbons (ACs) and the consecutive in situ regeneration of carbon by Fenton oxidation. Two different operations have been carried out: (1) a batch procedure in order to investigate the influence of Fe2+ and H2O2 concentrations; (2) continuous fixed bed adsorption, followed by a batch circ...

The quick development of the industry and the society runs parallel with the increasing generation of wastewaters, with the presence of highly toxic and low biodegradable compounds. This situation represents a problem for the conventional biological treatments; the most used process in wastewater treatment. The appearance of the so named "emergent...

Direct aqueous carbonation is a promising mineral carbonation route. Under mildly acidic conditions, this single-step carbonation process aims to simultaneously dissolve Ca/Mg-bearing silicates or wastes and precipitate Ca/Mg carbonates. By and large, since mineral dissolution is rate limiting due to the lack of protons at near-neutral pH, research...

A sequential process for water treatment involving usual adsorption on activated carbon (AC) followed by wet air catalytic oxidation of the adsorbed pollutants has been carried out in a fixed bed reactor with a mixture of two model pollutants. The first step achieves water purification while the second one reduces the organic pollution but also, mo...

Adsorption on activated carbon has been successfully used in wastewater and drinking water treatment plants for the removal of various pollutants. Among them, pharmaceutical compounds have become a growing issue. The present study has focused on levodopa molecule, which is one of the drugs used to treat symptoms of Parkinson’s disease. The adsorpti...

An experimental parametric study on wetting efficiency is reported which evaluates the influence of liquid viscosity, as well as the effect of particle size(/shape) and bed porosity (εB), separately. A 10-fold increase of liquid viscosity improves slightly catalyst wetting (by about 10%), while an increase of either bed porosity or particle size ha...

Since the past decade, ionic liquids have gained significant importance as alternative solvents for catalysis applications. Many of the reactions evaluated in ionic liquids employ gases as substrates, and therefore it is important to know their solubility and mass transfer characteristics. This work reports for the first time both the solubility an...

Since the past decade, ionic liquids have gained significant importance as alternative solvents for catalysis applications. Many of the reactions evaluated in ionic liquids employ gases as substrates, and therefore it is important to know their solubility and mass transfer characteristics. This work reports for the first time both the solubility an...

Pharmaceutical products are often present in wastewater treatment effluents, rivers, lakes and, more rarely, in groundwater. The advanced oxidation methods, like ultrasound, find a promising future in the area of wastewater treatment. The aim of this paper is to evaluate the influence of several parameters of the ultrasound process on the degradati...

The wetting efficiency of liquid trickle flow over a fixed bed reactor has been measured for a wide range of parameters including operating conditions, bed structure and physico-chemistry of liquid/solid phases. This data bank has been used to develop a new correlation for averaged wetting efficiency based on five different non-dimensional numbers....

Catalytic Wet Air Oxidation (CWAO) has been investigated for the treatment of water contaminated by 4-hydroxybenzoic acid (4HBA). Both batch measurements for kinetics determination and continuous trickle bed operation have been performed on the same Activated Carbon (AC). After a fast initial deactivation AC was proved stable and efficient at moder...

Catalytic Wet Air Oxidation (CWAO) has been investigated for the treatment of water contaminated by 4-hydroxybenzoic acid (4HBA) and equimolar mixture of phenol-4HBA. Both batch measurements for kinetics determination and continuous fixed bed operation have been performed on the same Activated Carbon (AC). After a fast initial deactivation AC was p...

This work investigates the tracer technique for the measurement of catalyst wetting efficiency, f, in trickle-bed reactor. The model of Ramachandran et al. (1986), based on a 2D description of the tracer diffusion, is applied for the full range of wetting efficiency. It is also extended to account for the effects of axial dispersion, liquidsolid ma...

Local and average partial wetting efficiencies in trickle-beds have been directly measured by image processing and PIV analysis. Two different setups have been implemented: a vertical monolayer of pellets where the wetting structure and stability and also local velocity gradient are characterized by PIV, and a fixed bed to analyze (by photography)...

Three very different techniques for measuring the catalyst wetted fraction -or wetting efficiency- in trickle bed reactors have been carried out and compared. The first one based on pressure drop data performed successively in single gas then liquid phase, then in gas-liquid phase is experimentally very simple but did not result in meaningful wetti...

On a cherché à quantifier et comprendre l’effet de particules microniques sur le transfert de matière gaz-liquide. Les mesures ont été réalisées à la fois en colonne à bulles et en réacteur agité par une turbine à induction de gaz pour des suspensions de nature (charbons, silices hydrophiles et hydrophobisées), de taille (de 4 à 32 μm) et de concen...

Un traitement d’images, issues de cinématographie rapide en colonne 2D, donne la distribution de taille de bulles d’air dans l’eau pure ou additivée. La technique, basée sur l’analyse de nombreuses bulles, nécessitant leur identification et leur suivi en cas de rupture ou coalescence, est tout d abord décrite puis utilisée pour préciser l’influence...

The wet air oxidation of phenol over a commercial active carbon catalyst has been studied in laboratory and pilot plant Fixed Bed Reactors at mild temperatures and oxygen partial pressures of 120-160 ºC and 0.05-0.2 MPa, respectively. The performance of the Fixed Bed Reactors has been assessed and compared to each other for both up-and downflow ope...

De nombreux facteurs poussent à la réduction des vitesses superficielles de liquide dans les réacteurs catalytiques à lit fixe fonctionnant à co-courant descendant en régime ruisselant. Ces nouvelles conditions hydrodynamiques peuvent entraîner un mouillage partiel des grains de catalyseur. L’objectif de cette étude est d’observer et de quantifier...