Managing siloxanes in biogas-to-energy facilities: Economic comparison of pre- vs post-combustion practices.

Siloxanes present in small concentrations in biogas interfere with the operation of biogas-to-energy facilities. During biogas combustion, siloxanes form white deposits on engine components (engine heads, spark plugs, valves) in crystals or amorphous forms depending on the temperature. The purpose of this study was to evaluate the economic feasibility of biogas-to-energy systems for managing the operational challenges due to siloxanes in biogas. The facility maintenance cost data were compiled by a survey of biogas-to-energy facilities in the United States. Economic analyses were performed to compare the operational costs due to increased maintenance for removing the white deposits forming on the engine components and the installation of a pretreatment system (carbon adsorption) to remove siloxanes prior to combustion. Numerical analyses showed that for the facilities with operating capacities less than 1300 m3/h (750 scfm), the costs for installation and operation of the carbon adsorption system exceeded the maintenance costs for removal of deposits from the engine components. The maintenance costs correlated well with the reported maintenance needs which were between 120 and 800 man hours per year. On the basis of siloxane removal costs alone, it is not economically feasible to install a carbon adsorption system for siloxane removal prior to combustion for small facilities processing less than 1300 m3/h (750 scfm) of biogas. However, using a process for siloxane removal prior to gas engines (e.g., carbon adsorption) would be improve the overall performance of the gas engines and reduce maintenance need at all facilities.

Selectivity and limitations of carbon sorption tubes for capturing siloxanes in biogas during field sampling.

Siloxane levels in biogas can jeopardize the warranties of the engines used at the biogas to energy facilities. The chemical structure of siloxanes consists of silicon and oxygen atoms, alternating in position, with hydrocarbon groups attached to the silicon side chain. Siloxanes can be either in cyclic (D) or linear (L) configuration and referred with a letter corresponding to their structure followed by a number corresponding to the number of silicon atoms present. When siloxanes are burned, the hydrocarbon fraction is lost and silicon is converted to silicates. The purpose of this study was to evaluate the adequacy of activated carbon gas samplers for quantitative analysis of siloxanes in biogas samples. Biogas samples were collected from a landfill and an anaerobic digester using multiple carbon sorbent tubes assembled in series. One set of samples was collected for 30min (sampling 6-L gas), and the second set was collected for 60min (sampling 12-L gas). Carbon particles were thermally desorbed and analyzed by Gas Chromatography Mass Spectrometry (GC/MS). The results showed that biogas sampling using a single tube would not adequately capture octamethyltrisiloxane (L3), hexamethylcyclotrisiloxane (D3), octamethylcyclotetrasiloxane (D4), decamethylcyclopentasiloxane (D5) and dodecamethylcyclohexasiloxane (D6). Even with 4 tubes were used in series, D5 was not captured effectively. The single sorbent tube sampling method was adequate only for capturing trimethylsilanol (TMS) and hexamethyldisiloxane (L2). Affinity of siloxanes for activated carbon decreased with increasing molecular weight. Using multiple carbon sorbent tubes in series can be an appropriate method for developing a standard procedure for determining siloxane levels for low molecular weight siloxanes (up to D3). Appropriate quality assurance and quality control procedures should be developed for adequately quantifying the levels of the higher molecular weight siloxanes in biogas with sorbent tubes.

Evaluation of a Full-Scale Water-Based Scrubber for Removing Siloxanes from Digester Gas: A Case Study.

Siloxanes are becoming more prominent in digester gas at water resource recovery facilities because of their wide use in personal care products. This study evaluates a full-scale water-based scrubber operating in a water resource recovery facility (Miami, FL). The digester gas is used for energy generation due to its high methane content. During energy generation, siloxanes are converted to silicates and Silicon Dioxide (SiO2), which leave deposits on engine components. Trimethylsilanol (TMSOH), Octamethyltrisiloxane (L3), Hexamethylcyclotrisiloxane (D3), Octamethylcyclotetrasiloxane (D4), Decamethylcyclopentasiloxane (D5), and Dodecamethylcyclohexasiloxane (D6) were detected in the digester gas. D4 and D5 were present at the highest concentrations, 5000 and 1800 µg/ m3, respectively. Sampling results have indicated that scrubbers employed for hydrogen sulfide (H2S) removal at the facility do not provide effective removal of siloxanes due to their high Henry's Constant. Post scrubber treatment is needed to remove siloxanes from the digester gas prior to combustion.

Contribution of siloxanes to COD loading at wastewater treatment plants: phase transfer, removal, and fate at different treatment units.

Cyclic volatile methylsiloxanes (cVMSs) are entering to waste stream in increasing quantities due to their increasing use in personal care products (i.e., shampoos, creams). The cVMSs have high vapor pressures and low solubilities and are mostly transferred into the gaseous phase via volatilization; however, some are sorbed onto biosolids. The purpose of this study was to track and estimate the phase transfer (water, solids, gas), fate, and contribution to COD loading of selected siloxanes (D4, D5 and D6) which are the most commonly found cVMSs in the wastewater systems. Removal efficiencies of the wastewater treatment units were evaluated based on the partitioning characteristics of the cVMSs in gas, liquid, and biosolids phases. The contributions of the siloxanes present in the influent and effluent were estimated in terms of COD levels based on the theoretical oxygen demand (ThOD) of the siloxanes. Siloxanes constitute approximately 39 and 0.001mgL(-1) of the COD in the influents and effluent. Oxidation systems showed higher removal efficiencies based COD loading in comparison to the removal efficiencies achieved aeration tanks and filtration systems. Treatment systems effectively remove the siloxanes from the aqueous phase with over 94% efficiency. About 50% of the siloxanes entering to the wastewater treatment plant accumulate in biosolids.

Differences in volatile methyl siloxane (VMS) profiles in biogas from landfills and anaerobic digesters and energetics of VMS transformations.

The objectives of this study were to compare the types and levels of volatile methyl siloxanes (VMS) present in biogas generated in the anaerobic digesters and landfills, evaluate the energetics of siloxane transformations under anaerobic conditions, compare the conditions in anaerobic digesters and municipal solid waste (MSW) landfills which result in differences in siloxane compositions. Biogas samples were collected at the South District Wastewater Treatment Plant and South Dade Landfill in Miami, Florida. In the digester gas, D4 and D5 comprised the bulk of total siloxanes (62% and 27%, respectively) whereas in the landfill gas, the bulk of siloxanes were trimethylsilanol (TMSOH) (58%) followed by D4 (17%). Presence of high levels of TMSOH in the landfill gas indicates that methane utilization may be a possible reaction mechanism for TMSOH formation. The free energy change for transformation of D5 and D4 to TMSOH either by hydrogen or methane utilization are thermodynamically favorable. Either hydrogen or methane should be present at relatively high concentrations for TMSOH formation which explains the high levels present in the landfill gas. The high bond energy and bond distance of the Si-O bond, in view of the atomic sizes of Si and O atoms, indicate that Si atoms can provide a barrier, making it difficult to break the Si-O bonds especially for molecules with specific geometric configurations such as D4 and D5 where oxygen atoms are positioned inside the frame formed by the large Si atoms which are surrounded by the methyl groups.

A multiphase analysis of partitioning and hazard index characteristics of siloxanes in biosolids.

Siloxanes are widely used in personal care and industrial products due to their soft texture, low surface tension, thermal stability, antimicrobial and hydrophobic properties, among other characteristics. As a result, they are released to gas phase during waste decompositions and found in biogas at landfills and digester gas at wastewater treatment facilities. The objectives of this study were to investigate the release of siloxanes in aqueous and gaseous phase as well as in biosolids in a local wastewater treatment facility. The formation reactions were estimated using first order kinetics for commonly found siloxanes (L3, D3, D4, D5 and D6) during waste decomposition. Expected concentrations and the risk factors of exposure to siloxanes were evaluated based on the initial concentrations, partitioning characteristics and persistence parameter. D4 and D5 presented the highest initial gaseous phase concentrations of 5000 and 1800 µg/m(3) respectively. Based on first order kinetics, partition coefficients and initial concentrations, the hazards potentials were largest for D4 in both liquid phase and biosolids while D6 poses the highest risk in gaseous phase.

Oxidation of siloxanes during biogas combustion and nanotoxicity of Si-based particles released to the atmosphere.

Siloxanes have been detected in the biogas produced at municipal solid waste landfills and wastewater treatment plants. When oxidized, siloxanes are converted to silicon oxides. The objectives of this study were to evaluate the transformation of siloxanes and potential nanotoxicity of Si-based particles released to the atmosphere from the gas engines which utilize biogas. Data available from nanotoxicity studies were used to assess the potential health risks associated with the inhalation exposure to Si-based nanoparticles. Silicon dioxide formed from siloxanes can range from 5 nm to about 100 nm in diameter depending on the combustion temperature and particle clustering characteristics. In general, silicon dioxide particles formed during from combustion process are typically 40-70 nm in diameter and can be described as fibrous dusts and as carcinogenic, mutagenic, astmagenic or reproductive toxic (CMAR) nanoparticles. Nanoparticles deposit in the upper respiratory system, conducting airways, and the alveoli. Size ranges between 5 and 50 nm show effective deposition in the alveoli where toxic effects are higher. In this study the quantities for the SiO2 formed and release during combustion of biogas were estimated based on biogas utilization characteristics (gas compositions, temperature). The exposure to Si-based particles and potential effects in humans were analyzed in relation to their particle size, release rates and availability in the atmosphere. The analyses showed that about 54.5 and 73 kg/yr of SiO2 can be released during combustion of biogas containing D4 and D5 at 14.1 mg/m(3) (1 ppm) and 15.1 mg/m(3) (1ppm), respectively, per MW energy yield.

Emergence and fate of cyclic volatile polydimethylsiloxanes (D4, D5) in municipal waste streams: release mechanisms, partitioning and persistence in air, water, soil and sediments.

Siloxane use in consumer products (i.e., fabrics, paper, concrete, wood, adhesive surfaces) has significantly increased in recent years due to their excellent water repelling and antimicrobial characteristics. The objectives of this study were to evaluate the release mechanisms of two siloxane compounds, octamethylcyclotetrasiloxane (D4) and decamethylcyclopentasiloxane (D5), which have been detected both at landfills and wastewater treatment plants, estimate persistence times in different media, and project release quantities over time in relation to their increasing use. Analyses were conducted based on fate and transport mechanisms after siloxanes enter waste streams. Due to their high volatility, the majority of D4 and D5 end up in the biogas during decomposition. D5 is about ten times more likely to partition into the solid phase (i.e., soil, biosolids). D5 concentrations in the wastewater influent and biogas are about 16 times and 18 times higher respectively, in comparison to the detected levels of D4.