Sylvain Giraudet

Different families of volatile organic compounds pollution control by microporous carbons in temperature swing adsorption processes

In this research work, the three different VOCs such as acetone, dichloromethane and ethyl formate (with corresponding families like ketone, halogenated-organic, ester) are recovered by using temperature swing adsorption (TSA) process. The vapors of these selected VOCs are adsorbed on a microporous activated carbon. After adsorption step, they are regenerated under the same operating conditions by hot nitrogen regeneration. In each case of regeneration, Factorial Experimental Design (FED) tool had been used to optimize the temperature, and the superficial velocity of the nitrogen for achieving maximum regeneration efficiency (R(E)) at an optimized operating cost (OP(€)). All the experimental results of adsorption step and hot nitrogen regeneration step had been validated by the simulation model PROSIM. The average error percentage between the simulation and experiment based on the mass of adsorption of dichloromethane was 3.1%. The average error percentages between the simulations and experiments based on the mass of dichloromethane regenerated by nitrogen regeneration were 4.5%.

Visualization of the exothermal VOC adsorption in a fixed-bed activated carbon adsorber

Activated carbon fixed beds are classically used to remove volatile organic compounds (VOCs) present in gaseous emissions. In such use, an increase of local temperature due to exothermal adsorption has been reported; some accidental fires in the carbon bed due to the removal of high concentrations of ketones have been published. In this work, removal of VOCs was performed in a laboratory-scale pilot unit. In order to visualize the increase in local temperature, the adsorption front was tracked with a flame ionization detector and the thermal wave was simultaneously visualized with an infrared camera. In extreme conditions, fire in the adsorber and the combustion of activated carbon was achieved during ketone adsorption. Data have been extracted from these experiments, including local temperature, front velocity and carbon bed combustion conditions.

Recovery comparisons—Hot nitrogen Vs steam regeneration of toxic dichloromethane from activated carbon beds in oil sands process

The regeneration experiments of dichloromethane from activated carbon bed had been carried out by both hot nitrogen and steam to evaluate the regeneration performance and the operating cost of the regeneration step. Factorial Experimental Design (FED) tool had been implemented to optimize the temperature of nitrogen and the superficial velocity of the nitrogen to achieve maximum regeneration at an optimized operating cost. All the experimental results of adsorption step, hot nitrogen and steam regeneration step had been validated by the simulation model PROSIM. The average error percentage between the simulation and experiment based on the mass of adsorption of dichloromethane was 2.6%. The average error percentages between the simulations and experiments based on the mass of dichloromethane regenerated by nitrogen regeneration and steam regeneration were 3 and 12%, respectively. From the experiments, it had been shown that both the hot nitrogen and steam regeneration had regenerated 84% of dichloromethane. But the choice of hot nitrogen or steam regeneration depends on the regeneration time, operating costs, and purity of dichloromethane regenerated. A thorough investigation had been made about the advantages and limitations of both the hot nitrogen and steam regeneration of dichloromethane.

Modeling the Temperature Dependence of Adsorption Equilibriums of VOC(s) onto Activated Carbons

In order to optimize the efficiency of the removal of volatile organic compounds (VOCs) by adsorption onto activated carbon beds, process simulations taking into account exothermicity effects are helpful. Significant temperature increases may arise in the bed during the VOC adsorption cycle, especially when high concentrations have to be treated. Consequently, reliable and easy-to-handle isotherms remain a key hurdle to build realistic models. In this study, adsorption models were tested to describe a set of experimental data obtained for three VOCs (acetone, ethyl formate, and dichloromethane) adsorbed onto five commercial activated carbons at four different temperatures (20, 40, 60, and 80°C ). A new expression of the Freundlich equation [ qe = ( a1 T+ a2 T2 ) Ce ( 1/ nf ) ] was shown to be statistically the most efficient to describe the adsorption isotherms of VOCs, single or in mixtures. A second-order polynomial temperature-dependence was introduced in this expression. The so-adapted Freundlich rela...

Hazardous dichloromethane recovery in combined temperature and vacuum pressure swing adsorption process.

Organic vapors emitted from solvents used in chemical and pharmaceutical processes, or from hydrocarbon fuel storage stations at oil terminals, can be efficiently captured by adsorption onto activated carbon beds. To recover vapors after the adsorption step, two modes of regeneration were selected and could be possibly combined: thermal desorption by hot nitrogen flow and vacuum depressurization (VTSA). Because of ignition risks, the conditions in which the beds operate during the adsorption and regeneration steps need to be strictly controlled, as well as optimized to maintain good performances. In this work, the optimal conditions to be applied during the desorption step were determined from factorial experimental design (FED), and validated from the process simulation results. The regeneration performances were compared in terms of bed regeneration rate, concentration of recovered volatile organic compounds (VOC) and operating costs. As an example, this methodology was applied in case of dichloromethane. It has been shown that the combination of thermal and vacuum regeneration allows reaching 82% recovery of dichloromethane. Moreover, the vacuum desorption ended up in cooling the activated carbon bed from 93°C to 63°C and so that it significantly reduces the cooling time before starting a new cycle.

Competitive adsorption of fluoride and natural organic matter onto activated alumina

ABSTRACT Natural organic matter (NOM) is a major water constituent that affects the performance of water treatment processes. Several studies have shown that NOM can be adsorbed on the surface of oxides and may compete with other ions. The overall goal of this study was essentially to investigate the competitive adsorption between fluoride and NOM on activated alumina (AA). For this purpose, a humic acid (HA) was used as a model compound for NOM. The interaction of NOM with fluoride, the simultaneous competitive adsorption, and the effect of preloading AA with NOM were investigated. The specific absorbance of HA was determined at 254 nm. Size-exclusion chromatography measurements confirmed the adsorption of aromatic fractions of NOM onto AA. The presence of HA in the system inhibited fluoride sorption onto AA and the removal yield using fresh AA decreased from 70.4 % to 51.0 % in the presence of HA. The decrease was more pronounced using AA preloaded with HA, reaching 37.7 %. The interference of coexisting ions and their effect on fluoride removal capacity were evaluated, showing a severe impact of the presence of phosphate on the removal capacity unlike nitrates and sulfates, which slightly improved the fluoride sorption.

Global statistical predictor model for characteristic adsorption energy of organic vapors–solid interaction: Use in dynamic process simulation

Adsorption of Volatile Organic Compounds (VOCs) is one of the best remediation techniques for controlling industrial air pollution. In this paper, a quantitative predictor model for the characteristic adsorption energy (E) of the Dubinin-Radushkevich (DR) isotherm model has been established with R(2) value of 0.94. A predictor model for characteristic adsorption energy (E) has been established by using Multiple Linear Regression (MLR) analysis in a statistical package MINITAB. The experimental value of characteristic adsorption energy was computed by modeling the isotherm equilibrium data (which contain 120 isotherms involving five VOCs and eight activated carbons at 293, 313, 333, and 353 K) with the Gauss-Newton method in a statistical package R-STAT. The MLR model has been validated with the experimental equilibrium isotherm data points, and it will be implemented in the dynamic adsorption simulation model PROSIM. By implementing this model, it predicts an enormous range of 1200 isotherm equilibrium coefficients of DR model at different temperatures such as 293, 313, 333, and 353K (each isotherm has 10 equilibrium points by changing the concentration) just by a simple MLR characteristic energy model without any experiments.

9 – Activated carbon filters for filtration–adsorption

The objectives of this chapter are to present gas and liquid filtrations, mainly focussing on the adsorption of organic compounds from fluids onto activated carbon fibers in their different forms (cloth, felts, knitted). The separation of target organics in complex mixtures and/or the purification of fluids (water, wastewater, air, biogas) are challenging. Different aspects are presented in order to describe the overall adsorption processes. The fluid flow patterns (aerodynamics or hydrodynamics) are shown according to the design of the adsorbers, and pressure drops are evaluated and modeled. For filtration–adsorption treatments, the main targets are volatile organic compounds or odorous molecules in air and organic micropollutants at trace levels in water. The designs and characteristics of these filters are presented through their performance in separation or purification as a function of operating conditions. Classic equations to model batch reactor isotherm curves or dynamic filter breakthrough curves are given and discussed. Some industrial achievements illustrate specific applications for water and air treatments. Lastly, future trends are presented.

Use of laterite as a sustainable catalyst for removal of fluoroquinolone antibiotics from contaminated water

Although there is a growing interest in Fenton oxidation processes based on natural catalysts, the use of laterite soil to promote sequential adsorption/oxidation treatments of fluoroquinolone antibiotics has been scarcely investigated. In this work, the ability of an african laterite containing goethite and hematite to remove flumequine (FLU), used as a representative compound of fluoroquinolone antibiotics, was evaluated under dark and UVA irradiation. Batch experiments and liquid chromatography analyses showed that the presence of laterite can enhance FLU removal from heavily contaminated water through both sorption and oxidation reactions (up to 94% removal of 77 μmol L-1 of FLU and 72% of mineralization). The heterogeneous reaction rate is dominated by the rate of intrinsic surface chemical reactions including sorption and oxidation of FLU, and light-induced reduction of FeIII sites to produce FeII. Based on the probe and scavenging experiments, OH radicals were mainly involved in the heterogeneous oxidation reaction. The photo-assisted Fenton process showed a high efficiency of FLU removal even in the presence of a second fluoroquinolone antibiotic, norfloxacin (NOR), which can be co-found with FLU in affected environments. Determinations of kinetic rate constants and total organic carbon (TOC) for five sequential adsorption/oxidation cycles showed that laterite exhibited no deactivation of surface sites and an excellent catalytic stability. This cost-effective and environmentally friendly remediation technology may appear as a promising way for the removal of fluoroquinolone antibiotics from multi-contaminated waters.

1H NMR Investigations of Activated Carbon Loaded with Volatile Organic Compounds: Quantification, Mechanisms, and Diffusivity Determination

Three volatile organic compounds (VOCs), benzene, cyclohexane, and dichloromethane, were adsorbed onto activated carbon fiber cloth. 1H (magic-angle spinning (MAS) and pulsed field gradient (PFG)) NMR techniques were carried out, and the signals were analyzed in terms of peak surface areas and shifts. These techniques were shown to be very useful for determining (i) the intrinsic quantification of adsorbed molecules (VOCs and/or water) in the porosity of the materials (the adsorption capacities ranged from 0.2 to 4 mol·kg-1); (ii) the mechanisms of interactions between adsorbed organic molecules and the carbon walls (illustrations of positions of the molecule inside the pore volume are proposed; the proton-wall distance was less than 0.15 nm); and (iii) the diffusivities (surface diffusion coefficients (DS) were estimated at ≈4.10-12 m2·s-1 for cyclohexane, ≈1.10-11 m2·s-1 for benzene, and ≈4.10-11 m2·s-1 for dichloromethane).