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.

Assessment of MSWI bottom ash organic carbon behavior: a biophysicochemical approach.

In order to understand the influence of organic components on the behavior of municipal solid waste incinerator bottom ash, samples from five French incinerators have been analyzed and compared. Biological and physico-chemical experiments were coupled with a view to developing a new rapid assessment method of bottom ash quality. Bottom ash had different total organic carbon contents ranging from 8.8 g kg(-1) to 37.4 g kg(-1). A part of this organic carbon can be leached into the environment or provide a substrate for microbial activity. Samples showed really different behaviors regarding these processes. Comparative results of leaching tests and biodegradation experiments showed a positive correlation between dissolved organic carbon and microbial activity. However, quantities of biodegraded or leached carbon are not representative of the samples' total organic carbon content. Thermal analyses in oxidizing conditions have revealed the presence of two fractions of organic components, showing different thermal behaviors. The associated mass losses were measured and compared to dissolved organic carbon. One of the two fractions can be directly linked to the leachable and easily biodegradable organic matter fraction. Calorimetric test is then presented as a novel analysis method that allows to provide rapid and global information concerning the characteristics of organic matter in bottom ash and its possible short and long-term evolution.

Influence of waste input and combustion technology on MSWI bottom ash quality.

The waste input and the process technology of waste incineration plants appear to have a great influence on bottom ash quality. To better understand how these parameters can affect the characteristics of residues, bottom ash from six plants were tested and compared in this study. Bottom ash physico-chemical characteristics were investigated by chemical analyses, and leaching tests. In order to understand their long-term behavior, accelerated ageing experiments and biodegradation tests were also performed. The whole analyses gave complementary information. It was shown that the six samples do have different properties. Waste inputs have a great influence on Cl and S content in bottom ash, as well as on the Ca/Si ratio. The importance of this ratio on the carbonation process has been demonstrated. Combustion parameters have an influence on the quantity and mobility of the residual organic matter.

Influence of organic matter on municipal solid waste incinerator bottom ash carbonation.

The biodegradation of organic matter in municipal solid waste incinerator (MSWI) bottom ash was studied in order to investigate the interaction between the CO(2) produced by microbial respiration and bottom ash. Respiration tests were performed on bottom ash at different moisture contents in an incubator at 30 degrees C. O(2) consumption and CO(2) production were monitored and quantified. Leaching tests were carried out at the end of the experiments. Total organic carbon (TOC) leaching had decreased. Over a period of three weeks, pH decreased from 10.7 to 8.2 and bottom ash was considered to be fully carbonated. This showed that the organic matter found in bottom ash can provide a substrate for microbial activity. The CO(2) produced by microbial respiration was directly dissolved in bottom ash pore water in order to be mineralized in carbonate form. The origin of the carbon dioxide which induces maturation of bottom ash on weathering areas has never been really discussed and is often presumed to be atmospheric CO(2). However, biodegradation of organic matter could contribute for a large part to this phenomenon, depending on field-scale physico-chemical weathering conditions.

Carbon dioxide sequestration in municipal solid waste incinerator (MSWI) bottom ash.

During bottom ash weathering, carbonation under atmospheric conditions induces physico-chemical evolutions leading to the pacification of the material. Fresh bottom ash samples were subjected to an accelerated carbonation using pure CO2. The aim of this work was to quantify the volume of CO2 that could be sequestrated with a view to reduce greenhouse gas emissions and investigate the possibility of upgrading some specific properties of the material with accelerated carbonation. Carbonation was performed by putting 4mm-sieved samples in a CO2 chamber. The CO2 pressure and the humidity of the samples were varied to optimize the reaction parameters. Unsieved material was also tested. Calcite formation resulting from accelerated carbonation was investigated by thermogravimetry and differential scanning calorimetry (TG/DSC) and metal leaching tests were performed. The volume of sequestrated CO2 was on average 12.5L/kg dry matter (DM) for unsieved material and 24 L/kg DM for 4mm-sieved samples. An ash humidity of 15% appeared to give the best results. The reaction was drastically accelerated at high pressure but it did not increase the volume of sequestrated CO2. Accelerated carbonation, like the natural phenomenon, reduces the dangerous nature of the material. It decreases the pH from 11.8 to 8.2 and causes Pb, Cr and Cd leaching to decrease. This process could reduce incinerator CO2 emissions by 0.5-1%.

Comparison of adsorbents for H2S and D4 removal for biogas conversion in a solid oxide fuel cell.

Biogas contains trace compounds detrimental for solid oxide fuel cell (SOFC) application, especially sulphur-containing compounds and volatile organic silicon compounds (VOSiCs). It is therefore necessary to remove these impurities from the biogas for fuelling an SOFC. In this paper, dynamic lab-scale adsorption tests were performed on synthetic polluted gas to evaluate the performance of a polishing treatment to remove hydrogen sulphide (H2S - sulphur compound) and octamethylcyclotetrasiloxane (D4 - VOSiC). Three kinds of adsorbents were tested: an activated carbon, a silica gel (SG) and a zeolite (Z). Z proved to be the best adsorbent for H2S removal, with an adsorbed quantity higher than [Formula: see text] at the SOFC tolerance limit. However, as concerns D4 removal, SG was the most efficient adsorbent, with an adsorbed quantity of about 184 mgD4/gSG at the SOFC tolerance limit. These results could not be explained by structural characteristics of the adsorbents, but they were partly explained by chemical interactions between the adsorbate and the adsorbent. In these experiments, internal diffusion was the controlling step, Knudsen diffusion being predominant to molecular diffusion. As Z was also a good adsorbent for D4 removal, competition phenomena were investigated with Z for the simultaneous removal of H2S and D4. It was shown that H2S retention was dramatically decreased in the presence of D4, probably due to D4 polymerization resulting in pore blocking.

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.