Pierre-François Biard

Intensification of volatile organic compounds mass transfer in a compact scrubber using the O3/H2O2 advanced oxidation process: kinetic study and hydroxyl radical tracking.

This study assesses the potential of ozonation and advanced oxidation process O(3)/H(2)O(2) to enhance the dimethyldisulfide (DMDS) mass transfer in a compact chemical scrubber developed for air treatment applications. Theoretical calculations, through Hatta number and enhancement factor evaluations for two parallel irreversible reactions, were compared to experimental data and enabled the description of the mass transfer mechanisms. These calculations required the determination of the kinetic constant of the DMDS oxidation by molecular ozone ( [Formula: see text] ) and the measurement of the hydroxyl radical concentration within the scrubber. The competitive kinetic method using the 1,2-dihydroxybenzene (resorcinol) enabled to determine a value of the kinetic constant [Formula: see text] of 1.1×10(6)M(-1)s(-1) at 293K. Then, experiments using para-chlorobenzoic acid in solution allowed measuring the average hydroxyl concentration in the scrubber between the inlet and the outlet depending on the chemical conditions (pH and inlet O(3) and H(2)O(2) concentrations). High hydroxyl radical concentrations (10(-8)M) and ratio of the HO°-to-O(3) exposure (R(ct)≈10(-4)) were put in evidence.

Assessment and optimisation of VOC mass transfer enhancement by advanced oxidation process in a compact wet scrubber

Dimethyl disulphide (DMDS) removal was investigated in a compact scrubber (hydraulic residence time approximately 20ms), composed of a wire mesh packing structure where liquid and gas flow at co-current and high gas superficial velocity (>12m s(-1)). In order to regenerate the scrubbing liquid and to maintain a driving force in the scrubber, ozone and hydrogen peroxide were added to water since they allow the generation of nonselective and highly reactive species, hydroxyl radicals HO(). Three ways of reagent distribution were tested. The influence of several parameters (liquid flow rate(s), ozone flow rate, pH and reagent concentrations) was investigated. The best configuration was obtained when ozone is transferred in the scrubbing liquid before introduction at the top of the scrubber simultaneously with the hydrogen peroxide solution, allowing to generate hydroxyl radical in the scrubber. With this configuration, DMDS removal could be increased from 16% with water to 34% at the same gas and liquid flow rates in the scrubber showing the potentiality of advanced oxidation process.

Synthesis and toxicity evaluation of hydrophobic ionic liquids for volatile organic compounds biodegradation in a two-phase partitioning bioreactor

Synthesis of several hydrophobic ionic liquids (ILs), which might be selected as good candidates for degradation of hydrophobic volatile organic compounds in a two-phase partitioning bioreactor (TPPB), were carried out. Several bioassays were also realized, such as toxicity evaluation on activated sludge and zebrafish, cytotoxicity, fluoride release in aqueous phase and biodegradability in order to verify their possible effects in case of discharge in the aquatic environment and/or human contact during industrial manipulation. The synthesized compounds consist of alkylimidazoliums, functionalized imidazoliums, isoqinoliniums, triazoliums, sulfoniums, pyrrolidiniums and morpholiniums and various counter-ions such as: PF6(-), NTf2(-) and NfO(-). Toxicity evaluation on activated sludge of each compound (5% v/v of IL) was assessed by using a glucose uptake inhibition test. Toxicity against zebrafish and cytotoxicity were evaluated by the ImPACCell platform of Rennes (France). Fluoride release in water was estimated by regular measurements using ion chromatography equipment. IL biodegradability was determined by measuring BOD28 of aqueous samples (compound concentration,1mM). All ILs tested were not biodegradable; while some of them were toxic toward activated sludge. Isoquinolinium ILs were toxic to human cancerous cell lines. Nevertheless no toxicity was found against zebrafish Danio rerio. Only one IL released fluoride after long-time agitation.

Absorption of Hydrophobic Volatile Organic Compounds in Ionic Liquids and Their Biodegradation in Multiphase Systems

The coupling of absorption in a gas-liquid contactor and biodegradation in a two-phase partitioning bioreactor (TPPB) has been shown to be a promising technology for the removal of hydrophobic volatile organic compounds. The choice of the organic phase is crucial, and consequently only two families of compounds comply with the requested criteria, silicone oils and ionic liquids. These latter solvents appear especially promising owing to their absorption capacity towards hydrophobic compounds and their low volatility, as well as the possibility of IL tailoring, allowing a fine-tuning of their physicochemical properties, leading to a wide range of products with various characteristics. Some results on common ionic liquids are highlighted in this chapter: biodegradation rates reported by some authors show that phenol biodegradation in the presence of ILs is up to 40 % higher than those obtained in other multiphase reactors; there is a strong affinity of toluene and DMDS for imidazolium salts, [C4Mim][PF6] or [C4Mim][NTf2]. Performance improvements may be expected from the tailoring of ionic liquid structure, especially towards toxicity reduction. Positive results recorded after cell acclimation to target compounds let expect an important gain from more complex acclimation strategies, including microbial acclimation to both ionic liquids and pollutants.

Impact of activated sludge acclimation on the biodegradation of toluene absorbed in a hydrophobic ionic liquid

Classical hydrophobic ionic liquids such as 3-butyl-1-methylimidazolium bis(trifluoroethylsulfonyl)imide or 3-butyl-1-methylimidazolium hexafluorophosphate application, as a non-aqueous liquid phase in a two-partitioning bioreactor to biodegrade hydrophobic volatile organic compounds by activated sludge, have been already reported in the literature, especially when the activated sludge was beforehand acclimated to the targeted volatile organic compound. In this study, four hydrophobic ionic liquids were used as non-aqueous liquid phase in a two-phase partitioning bioreactor to biodegrade toluene using non-acclimated activated sludge. The preliminarily results allowed to select two ionic liquids, 1-octylisoquinolinium bis(trifluoromethylsulfonyl)imide and allyl-diethylsulfonium bis(trifluoromethylsulfonyl)imide. The activated sludge was acclimated to both toluene and the considered ionic liquid. The results were compared to those obtained with non-acclimated activated sludge. The use of non-acclimated activated sludge for toluene biodegradation led to long lag times and low biodegradation rates. Thus, the acclimation to toluene improved the biodegradation rates; however, acclimation to both toluene and ionic liquid did not result in a significant improvement in the biodegradation rate compared to an acclimation to toluene alone. The activated sludge acclimation had a positive impact on toluene biodegradation and allowed to totally overcome the inhibitory effect of the presence of ionic liquid. The most relevant acclimation strategy seems to be a prior acclimation to toluene, whereas acclimation to the non-aqueous liquid phase can be achieved during the culture, namely by performing successive batches for instance, or a continuous operation.

Simulation of hydrogen sulphide absorption in alkaline solution using a packed column

In this work, a simulation tool was developed for hydrogen sulphide (H2S) removal in an alkaline solution in packed columns working at countercurrent. Modelling takes into account the mass-transfer enhancement due to the reversible reactions between H2S and the alkaline species (, and HO−) in the liquid film. Many parameters can be controlled by the user such as the gas and liquid inlet H2S concentrations, the gas and liquid flow rates, the scrubbing liquid pH, the desired H2S removal efficiency, the temperature, the alkalinity, etc. Since the influence of the hydrodynamic and mass-transfer performances in a packed column is well known, the numerical resolutions performed were dedicated to the study of the influence of the chemical conditions (through the pH and the alkalinity), the temperature and the liquid-to-gas mass flow rate ratio (L/G). A packed column of 3 m equipped with a given random packing material working at countercurrent and steady state has been modelled. The results show that the H2S removal efficiency increases with the L/G, the pH, the alkalinity and more surprisingly with the temperature. Alkalinity has a very significant effect on the removal efficiency through the mass-transfer enhancement and buffering effect, which limits pH decreasing due to H2S absorption. This numerical resolution provides a tool for designers and researchers involved in H2S treatment to understand deeper the process and optimize their processes.