Patrick Germain

Biogas - municipal solid waste incinerator bottom ash interactions: sulphur compounds removal.

This study focuses on a new way of reusing municipal solid waste incinerator bottom ash: landfill gas purification before energetic valorisation. A pilot plant was designed and operated on a landfill site located in France (Loire). One kilogram bottom ash is able to sequestrate more than 3.0 g of hydrogen sulphide, 44 mg of methyl mercaptan, and 86 mg of dimethyl sulphide. Hydrogen sulphide retention is probably due to acid-basic reactions conducting to sulphur mineralisation under the form of low solubility metal sulphides. The reaction medium is hydration water. The retention mechanism for methyl mercaptan is probably similar but dimethyl sulphide is most likely retained by physical adsorption. As methane is not retained by bottom ash, the landfill gas energetic content will not be lowered. There seems to be no appreciable difference in these results whether bottom ash is fresh or carbonated. These results are encouraging in the perspective of a field scale application of this biogas treatment process.

Hydrolysis of polydimethylsiloxane fluids in controlled aqueous solutions.

Accelerated degradation tests were performed on polydimethylsiloxane (PDMS) fluids in aqueous solutions and in extreme chemical conditions (pH 2-4 and 9-12). Results confirmed that silicones can be degraded by hydrolysis. Higher degradation levels were achieved in very acidic and alkaline conditions. Degradation products are probably polar siloxanols. In alkaline conditions, the counter-ion was found to have a strong influence on degradation level. Degradation kinetic studies (46 days) were also performed at different pH values. Supposing zeroth-order kinetics, degradation rate constants at 24 °C were estimated to 0.28 mgSi L(-1) day(-1) in NaOH solution (pH 12), 0.07 mgSi L(-1) day(-1) in HCl solution (pH 2) and 0.002 mgSi L(-1) day(-1) in demineralised water (pH 6). From these results, the following hypothesis was drawn: PDMS hydrolysis could occur in wastewater treatment plants and in landfill cells. It may be a first step in the formation of volatile organic silicon compounds (VOSiCs, including siloxanes) in biogas: coupled to biodegradation and (self-) condensation of degradation products, it could finally lead to VOSiCs.

Silicone-based surfactant degradation in aqueous media

The increasing use of surfactants, such as modified polydimethylsiloxane-graft-polyethylene oxide (PDMS-g-PEO), requires studies on the fate of these compounds in the environment, and in particular in wastewater systems. A kinetic study, performed under three different pH conditions (pH2, 5.3 and 11) and using (1)H NMR (Nuclear Magnetic Resonance), proves that hydrolysis of the siloxane chain takes place in all cases, with higher rates for the two extreme conditions. Steric exclusion chromatography (SEC) clearly showed a decrease in the average molecular weight of the copolymer leading to a new molecular weight distribution, especially in acidic conditions. Degradation products, analyzed by (29)Si NMR, were found to be similar whatever the degradation pathway, namely silanediols and cyclic volatile compounds (degradation products of PDMS) and also PEO-modified silanediols and cyclic compounds. After one year, the siloxane chain completely disappeared under acidic conditions. Real wastewater medium has a strong effect on polymer stability, indicating that pH is not the only parameter which influences degradation rate.

Valorization of MSWI bottom ash for biogas desulfurization: Influence of biogas water content

In this study an alternative valorization of Municipal Solid Waste Incineration (MSWI) Bottom Ash (BA) for H2S elimination from landfill biogas was evaluated. Emphasis was given to the influence of water content in biogas on H2S removal efficiency by BA. A small-scale pilot was developed and implemented in a landfill site located in France. A new biogas analyzer was used and allowed real-time continuous measurement of CH4, CO2, O2, H2S and H2O in raw and treated biogas. The H2S removal efficiency of bottom ash was evaluated for different inlet biogas humidities: from 4 to 24gwater/m3. The biogas water content was found to greatly affect bottom ash efficiency regarding H2S removal. With humid inlet biogas the H2S removal was almost 3 times higher than with a dry inlet biogas. Best removal capacity obtained was 56gH2S/kgdryBA. A humid inlet biogas allows to conserve the bottom ash moisture content for a maximum H2S retention.

The effect of the origin of MSWI bottom ash on the H2S elimination from landfill biogas

Municipal Solid Waste Incineration (MSWI) Bottom Ash (BA) is a potential alternative adsorbent for biogas treatment due to its reactivity with hydrogen sulfide (H2S). The quality of BA depends however on the nature of the waste and the process technology of the waste incineration facility. To determine whether the origin of the BA could have an influence on its H2S elimination efficiency, comparative experimental tests were conducted in a landfill site with six bottom ashes from different MSW incinerators. Results showed that one of the BAs (A) had a much higher adsorption capacity than the rest (B-F), with 37g H2S/kg dry BA, compared to 11-16g H2S/kg dry BA for the other bottom ashes. Detailed physico-chemical analyses of the six BA were performed and complemented by principal component analysis to understand the different behaviors. BA iron content and specific surface area provided by the quench product stood out as key factors that promote the elimination of H2S.