Siloxanes removal from biogas by high surface area adsorbents

Biogas utilized for energy production needs to be free from organic silicon compounds, as their burning has damaging effects on turbines and engines; organic silicon compounds in the form of siloxanes can be found in biogas produced from urban wastes, due to their massive industrial use in synthetic product, such as cosmetics, detergents and paints.Siloxanes removal from biogas can be carried out by various methods (Mona, 2009, Ajhar et al., 2010, Schweigkofler and Niessner, 2001); aim of the present work is to find a single practical and economic way to drastically and simultaneously reduce both the hydrogen sulphide and the siloxanes concentration to less than 1 ppm. Some commercial activated carbons previously selected (Monteleone et al., 2011) as being effective in hydrogen sulfide up taking have been tested in an adsorption measurement apparatus, by flowing the most volatile siloxane (hexamethyldisiloxane or L2) in a nitrogen stream, typically 100–200 ppm L2 over N₂, through an activated carbon powder bed; the adsorption process was analyzed by varying some experimental parameters (concentration, grain size, bed height). The best activated carbon shows an adsorption capacity of 0.1 g L2 per gram of carbon. The next thermogravimetric analysis (TGA) confirms the capacity data obtained experimentally by the breakthrough curve tests.The capacity results depend on L2 concentration. A regenerative carbon process is then carried out by heating the carbon bed up to 200 °C and flushing out the adsorbed L2 samples in a nitrogen stream in a three step heating procedure up to 200 °C. The adsorption capacity is observed to degrade after cycling the samples through several adsorption–desorption cycles.     

Adsorption characteristics of siloxanes in landfill gas by the adsorption equilibrium test

Due to the increase in energy cost by constantly high oil prices and the obligation to reduce greenhouse effect gases, landfill gas is frequently used as an alternative energy source for producing heat and electricity. Most of landfill gas utility facilities, however, are experiencing problems controlling siloxanes from landfill gas as their catalytic oxidizers are becoming fouled by silicon dioxide dust. To evaluate adsorption characteristics of siloxanes, an adsorption equilibrium test was conducted and parameters in the Freundlich and Langmuir isotherms were analyzed. Coconut activated carbon (CA1), coal activated carbon (CA2), impregnated activated carbon (CA3), silicagel (NCA1), and activated alumina (NCA2) were used for the adsorption of the mixed siloxane which contained hexamethyldisiloxane (L2), octamethylcyclotetrasiloxane (D4), and decamethylcyclopentasiloxane (D5). L2 had higher removal efficiency in noncarbon adsorbents compared to carbon adsorbents. The application of Langmuir and Freundlich adsorption isotherm demonstrated that coconut based CA1 and CA3 provided higher adsorption capacity on L2. And CA2 and NCA1 provided higher adsorption capacity on D4 and D5. Based on the experimental results, L2, D4, and D5 were converted by adsorption and desorption in noncarbon adsorbents. Adsorption affinity of siloxane is considered to be affect by the pore size distribution of the adsorbents and by the molecular size of each siloxane.     

Life Cycle Assessment of landfill biogas management: Sensitivity to diffuse and combustion air emissions

Goal and scopeThe life cycle inventory of landfill emissions is a key point in Life Cycle Assessment (LCA) of waste management options and is highly subject to discussion. Result sensitivity to data inventory is accounted for through the implementation of scenarios that help examine how waste landfilling should be modeled in LCA.MethodFour landfill biogas management options are environmentally evaluated in a Life Cycle Assessment perspective: (1) no biogas management (open dump), conventional landfill with (2) flaring, (3) combined heat and power (CHP) production in an internal combustion engine and (4) biogas upgrading for use as a fuel in buses. Average, maximum and minimum literature values are considered both for combustion emission factors in flares and engines and for trace pollutant concentrations in biogas.ResultsBiogas upgrading for use as a fuel in buses appears as the most relevant option with respect to most non-toxic impact categories and ecotoxicity, when considering average values for trace gas concentrations and combustion emission factors. Biogas combustion in an engine for CHP production shows the best performances in terms of climate change, but generates significantly higher photochemical oxidant formation and marine eutrophication impact potentials than flaring or biogas upgrading for use as a fuel in buses.Interpretation and discussionHowever the calculated environmental impact potentials of landfill biogas management options depend largely on the trace gas concentrations implemented in the model. The use of average or extreme values reported in the literature significantly modifies the impact potential of a given scenario (up to two orders of magnitude for open dumps with respect to human toxicity). This should be taken into account when comparing landfilling with other waste management options. Also, the actual performances of a landfill top cover (in terms of oxidation rates) and combustion technology (in terms of emission factors) appear as key parameters affecting the ranking of biogas management options.     

Life-cycle greenhouse gas emissions and economic analysis of alternative treatments of solid waste from city markets in Vietnam

We utilize life cycle assessment to trace conversion of degradable organic carbon (DOC) contained in organic waste from city markets in Da Nang, Vietnam. Our methodology makes explicit the process of conversion of DOC under aerobic and anaerobic conditions, as well as the balance of nutrients. Greenhouse gas emissions were calculated for six alternative scenarios: (i) anaerobic landfilling (current situation); (ii) semi-aerobic landfilling; (iii) landfill gas capture; (iv) composting; (v) pre-composting before landfill; and (vi) biogas production. We calculate that 1 t of waste in anaerobic landfilling emits 1.70 t CO₂-eq. with life-cycle perspective. Lowest emission occurs in biogas scenario with 0.26 t CO₂-eq./t. Composting occupies an intermediate position with 0.39 t CO₂-eq./t. Likewise, we estimate that cost of emission reduction in solid waste sector of Vietnam is 15.13 US$/t CO₂-eq., given by alternative of composting and taking anaerobic landfilling as reference. On the other hand, if social cost of carbon (SCC) is incorporated lowest cost to treat 1 t of waste is given by composting and semi-aerobic landfilling at discount rate of 5 %. However, using lower discount rates, and consequently higher values of SCC, composting and biogas production become the alternatives with lowest treatment costs.     

Micrometeorological measurements of N2O and CH4 emissions from a municipal solid waste landfill.

Micrometeorological measurements of methane (CH4) and nitrous oxide (N2O) emissions were made at the decommissioned Park Road Landfill in Grimsby, Ontario, Canada between June and August 2002. The influence of precipitation, air temperature, wind speed and barometric pressure on the temporal variability of landfill biogas emissions was assessed. Gas flux measurements were obtained using a micrometeorological mass balance measurement technique [integrated horizontal flux (IHF)] in conjunction with two tunable diode laser trace gas analyser (TDLTGA) systems. This method allows for continuous, non-intrusive measurements of gas flux at high temporal resolution. Mean fluxes of N2O were negligible over the duration of the study (-0.23 to 0.02 microg m(-2) s(-1)). In contrast, mean emissions of CH4 were much greater (80.4 to 450.8 microg m(-2) s(-1)) and varied both spatially and temporally. Spatial variations in CH4 fluxes were observed between grass kill areas (biogas 'hot spots') and the densely grass-covered areas of the landfill. Temporal variations in CH4 fluxes were also observed, due at least in part to barometric pressure, wind speed and precipitation effects.     

Study of the VOC emissions from a municipal solid waste storage pilot-scale cell: comparison with biogases from municipal waste landfill site

The emission of volatile organic compounds (VOCs) from municipal solid waste stored in a pilot-scale cell containing 6.4 tonnes of waste (storage facility which is left open during the first period (40 days) and then closed with recirculation of leachates during a second period (100 days)) was followed by dynamic sampling on activated carbon and analysed by GC–MS after solvent extraction. This was done in order to know the VOC emissions before the installation of a methanogenesis process for the entire waste mass. The results, expressed in reference to toluene, were exploited during the whole study on all the analyzable VOCs: alcohols, ketones and esters, alkanes, benzenic and cyclic compounds, chlorinated compounds, terpene, and organic sulphides.The results of this study on the pilot-scale cell are then compared with those concerning three biogases from a municipal waste landfill: biogas (1) coming from waste cells being filled or recently closed, biogas (2) from all the waste storage cells on site, and biogas (3) which is a residual gas from old storage cells without aspiration of the gas. The analysis of the results obtained revealed: (i) a high emission of VOCs, principally alcohols, ketones and esters during the acidogenesis; (ii) a decrease in the alkane content and an increase in the terpene content were observed in the VOCs emitted during the production of methane; (iii) the production of heavier alkanes and an increase in the average number of carbon atoms per molecule of alkane with the progression of the stabilisation/maturation process were also observed.Previous studies have concentrated almost on the analysis of biogases from landfills. Our research aimed at gaining a more complete understanding of the decomposition/degradation of municipal solid waste by measuring the VOCs emitted from the very start of the landfill process i.e. during the acidogenesis and acetogenesis phases.     

Near-real-time measurement of trace volatile organic compounds from combustion processes using an on-line gas chromatograph

The US EPA's current regulatory approach for combustion and incineration sources considers the use of real-time continuous emission monitors (CEMs) for particulate, metals, and organic compounds to monitor source emissions. Currently, the CEM technologies to support this approach have not been thoroughly developed and/or demonstrated. The EPA's Air Pollution Prevention and Control Division has developed a near-real-time volatile organic compound (VOC) CEM, using an on-line gas chromatograph (OLGC), capable of measuring over 20 VOCs at concentrations typically present in well-operated combustion systems. The OLGC system consists of a sample delivery system, a sample concentrator, and a GC equipped with both flame ionization and electron capture detectors. Application of the OLGC system was initially demonstrated through participation in the 1995 US EPA/DOE CEM demonstration program. Additional work has improved system performance, including increased automation and improved calibration technique. During pilot-scale incineration testing, measurement performance was examined in detail through comparisons to various CEM performance criteria. Specifically, calibration error, calibration drift error, and system bias were examined as a function of full scale (absolute error) and gas concentration (relative error). Although OLGC measurement performance was not able to meet standard EPA CEM measurement performance criteria, measurement performance was encouraging. The system demonstrated the ability to perform hourly trace level VOC measurements (0–100 ppbv) for as many as 23 different VOCs with boiling points ranging from −23.7 to 180.5 °C at a known level of measurement performance. This system is a suitable alternative to VOC reference method measurements which may be performed only intermittently.     

Use of Fourier transform infrared spectrometry as a continuous emission monitor

This paper describes the use of a Fourier transfer infrared (FTIR) spectrometer, integrated with a sampling system and a control software, as a continuous emission monitor (CEM) for on-line measurement of most volatile organic and some inorganic compounds from various gas emissions. The time response of the system was tested experimentally, and can be approximated by a complete mixing model. In order to validate the measurement accuracy of the system, spiking tests are suggested. This paper discusses considerations in designing the spiking test and analyzing the spiking results. Field test results show that the FTIR-CEM has a stable performance and can be applied to stack emission monitoring, process monitoring, and unknown HAPs identification in many thermal treatment processes.     

Surrogate compounds for dioxins in incineration. A review

Dioxins, formed in any combustion process where carbon, oxygen and chlorine are present, are a subject of major interest due to their toxicity. Their measurement is very expensive and time consuming. In order to optimize the combustion process, on-line measurements of pollutants must be done. The use of surrogate compounds instead of dioxins seems to be a convenient method to overcome the aforementioned drawback. This work is a review of the literature dedicated to the possible surrogate compounds for dioxins; the relationships found were systematized and, in some cases, the available experimental data were used and original correlations were found. Correlation of surrogate compounds was found to be: incinerator, feedstock, process and sample point location specific. Amongst the possible surrogates, chlorobenzenes show real possibilities to be good indicators for toxic equivalent factors.     

Quantifying methane emission from fugitive sources by combining tracer release and downwind measurements – A sensitivity analysis based on multiple field surveys

Using a dual species methane/acetylene instrument based on cavity ring down spectroscopy (CRDS), the dynamic plume tracer dispersion method for quantifying the emission rate of methane was successfully tested in four measurement campaigns: (1) controlled methane and trace gas release with different trace gas configurations, (2) landfill with unknown emission source locations, (3) landfill with closely located emission sources, and (4) comparing with an Fourier transform infrared spectroscopy (FTIR) instrument using multiple trace gasses for source separation. The new real-time, high precision instrument can measure methane plumes more than 1.2 km away from small sources (about 5 kg h^?1) in urban areas with a measurement frequency allowing plume crossing at normal driving speed. The method can be used for quantification of total methane emissions from diffuse area sources down to 1 kg per hour and can be used to quantify individual sources with the right choice of wind direction and road distance. The placement of the trace gas is important for obtaining correct quantification and uncertainty of up to 36% can be incurred when the trace gas is not co-located with the methane source. Measurements made at greater distances are less sensitive to errors in trace gas placement and model calculations showed an uncertainty of less than 5% in both urban and open-country for placing the trace gas 100 m from the source, when measurements were done more than 3 km away. Using the ratio of the integrated plume concentrations of tracer gas and methane gives the most reliable results for measurements at various distances to the source, compared to the ratio of the highest concentration in the plume, the direct concentration ratio and using a Gaussian plume model. Under suitable weather and road conditions, the CRDS system can quantify the emission from different sources located close to each other using only one kind of trace gas due to the high time resolution, while the FTIR system can measure multiple trace gasses but with a lower time resolution.     

Laboratory-scale measurements of N2O and CH4 emissions from hybrid poplars (Populus deltoides x Populus nigra).

The purpose of this study was to determine whether or not young hybrid poplar (Populus deltoides x Populus nigra) could transport landfill biogas internally from the root zone to the atmosphere, thereby acting as conduits for landfill gas release. Fluxes of methane (CH4) and nitrous oxide (N2O) from the seedlings to the atmosphere were measured under controlled conditions using dynamic flux chambers and a tunable diode laser trace gas analyser (TDLTGA). Nitrous oxide was emitted from the seedlings, but only when extremely high soil N2O concentrations were applied to the root zone. In contrast, no detectable emissions of CH4 were measured in a similar experimental trial. Visible plant morphological responses, characteristic of flood-tolerant trees attempting to cope with the negative effects of soil hypoxia, were observed during the CH4 experiments. Leaf chlorosis, leaf abscission and adventitious roots were all visible plant responses. In addition, seedling survival was observed to be highest in the biogas 'hot spot' areas of a local municipal solid waste landfill involved in this study. Based on the available literature, these observations suggest that CH4 can be transported internally by Populus deltoides x Populus nigra seedlings in trace amounts, although future research is required to fully test this hypothesis.     

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.     

Development of a simple and sensitive method for the characterization of odorous waste gas emissions by means of solid-phase microextraction (SPME) and GC-MS/olfactometry

A solid-phase microextraction (SPME) method has been developed for the extraction of odorous compounds from waste gas. The enriched compounds were characterized by gas chromatography-mass spectrometry (GC-MS) and gas chromatography followed by simultaneous flame ionization detection and olfactometry (GC-FID/O). Five different SPME fiber coatings were tested, and the carboxen/polydimethylsiloxane (CAR/PDMS) fiber showed the highest ability to extract odorous compounds from the waste gas. Furthermore, parameters such as exposure time, desorption temperature, and desorption time have been optimized. The SPME method was successfully used to characterize an odorous waste gas from a fat refinery prior to and after waste gas treatment in order to describe the treatment efficiency of the used laboratory scale plant which consisted of a bioscrubber/biofilter combination and an activated carbon adsorber. The developed method is a valuable approach to provide detailed information of waste gas composition and complements existing methods for the determination of odors. However, caution should be exercised if CAR/PDMS fibers are used for the quantification of odorous compounds in multi-component matrices like waste gas emissions since the relative affinity of each analyte was shown to differ according to the total amount of analytes present in the sample.     

Effect of persistent trace compounds in landfill gas on engine performance during energy recovery: A case study

Performances of gas engines operated with landfill gas (LFG) are affected by the impurities in the LFG, reducing the economic viability of energy recovery. The purpose of this study was to characterize the trace compounds in the LFG at the Odayeri Landfill, Istanbul, Turkey which is used for energy recovery. Composite gas samples were collected and analyzed for trace compounds (hydrocarbons, siloxanes, and volatile halogenated hydrocarbons) over a 3-year period. Trace compounds entering the gas engines, their impact on the engine performance were evaluated. The operational problems included deposit formation in the combustion chamber, turbocharger, and intercooler of engine before the scheduled maintenance times. High levels of hydrogen sulfide, as well as chlorinated and fluorinated compounds cause corrosion of the engine parts and decrease life of the engine oils. Persistence of siloxanes results in deposit formation, increasing engine maintenance costs. Pretreatment of LFG is necessary to protect the engines at the waste-to-energy facilities with persistence levels of siloxanes and volatile halogenated hydrocarbons.     

Characterization of trace constituents in landfill gas and a comparison of sites in Asia

Because landfill gas (LFG) contains an abundance of methane, the utilization of LFG as a renewable energy source is becoming popular in many countries. LFG, however, contains various trace constituents, some of which may pose problems during utilization. For example, siloxanes and halogenated volatile organic compounds (VOCs) can cause difficulties when present in the fuel of gas engines. In addition, many VOCs and mercury have harmful effects on human health, especially on the health of workers at landfill sites and people living near the landfills. Energy recovery from LFG is expected to make great progress in the near future, particularly in Asia, but we found little information on the trace constituents of LFG in this region. Therefore, we sought to characterize the trace components in LFG generated in two landfill sites in China and one site in Japan, to determine the typical concentrations of these trace components in LFG, and to compare their concentrations among landfill sites in Asia. We concluded that the trace components in LFG at the sites studied were mainly siloxanes generated from sewage sludge and harmful benzene, toluene, ethylbenzene, and xylene compounds from petroleum products.     

Anaerobic co-digestion of municipal solid organic waste with melon residues to enhance biodegradability and biogas production

Management of solid organic waste has become a major challenge in developing countries. Raw solid organic waste can be converted into biogas through anaerobic digestion; however, the efficiency of the process is influenced by various factors including the composition of the substrate. The present study was designed with the objective of enhancing the biodegradability of the organic fraction of municipal solid waste (OFMSW) and biogas production through co-digestion of the substrate with melon residues. The study was conducted in batch mode in four phases. The results revealed that an addition of melon waste at the rate of 300?g?kg^?1 OFMSW substantially increased the biodegradation rate and biogas production compared to OFMSW alone. The removal of up to 57.2?% volatile solids and a carbon to nitrogen (C/N) ratio of 15.9 was achieved at a 60?% water level when the digestion mixture was treated with inocula collected from partially-degraded food waste. The findings of this study reveal that melon residues could be used as a potential co-substrate to enhance the biodegradability of OFMSW and biogas production.     

CHANGES IN MAJOR AND TRACE COMPONENTS OF LANDFILL GAS DURING SUBSURFACE MIGRATION

A gas plume emanating from the Foxhall Landfill in Suffolk (U.K.) has been defined within unsaturated ferruginous sands on the basis of elevated concentrations of methane, carbon dioxide and volatile organic compounds (VOCs). The plume is relatively narrow, extends more than 100 m from the landfill boundary, and lies mainly between 2 m bgl (below ground level) and the water table at 9.5 m bgl. With increasing distance along the axis of the plume, the ratio of methane to carbon dioxide gradually decreases, while nitrogen increases. Oxygen appears beyond 80 m from the landfill boundary. Stable carbon and hydrogen isotope ratios in methane become heavier with distance, while carbon dioxide becomes isotopically lighter with respect to stable carbon. This provides strong evidence for microbially mediated methane oxidation. Zones of black reduced sediment near the landfill suggest that ferric iron [Fe(III)] may be acting as an electron acceptor for oxidation. No thermal anomaly was observed, thus suggesting that the rate of oxidation/flux of methane is low. Volatile organic compounds in the plume were trapped using a combination of sorbants (Tenax GR, Haysep Q and Carbosieve S-III), and desorbed thermally into a GC/MS for semi-quantitative analysis. The 79 VOCs identified were similar to those found in other landfills, and their concentrations, both in the landfill and in the soil gas, were broadly related to their volatility. Only two compounds (vinyl chloride and dichlorofluoromethane) approached or exceeded the long-term exposure limit (LTEL, as defined by the U.K. Health and Safety Executive, 1992) outside the landfill. Halogenated compounds (dichlorodifluoromethane, dichlorofluoromethane and trichlorofluoromethane) were found to be most mobile but their concentration profiles suggest that they may have been flushed out of the landfill during its early stages. It is suggested that the association of volatile halogenated compounds with methane is good evidence that they are derived from a landfill.     

Factors related to the diversity and distribution of soil fauna on Gin Drinkers' Bay landfill,Hong Kong

The major potential problems from a landfill are biogas and leachate generated from the wastes deposited. These factors can also exert harmful effects on the growth of vegetation and influence the diversity and distribution of soil animals, either directly or indirectly. This paper describes investigations undertaken at the completed Gin Drinkers' Bay landfill, Hong Kong. The absence of plant cover at the site limited the occurrence of some common soil animals such has Diplopoda, Hemiptera, Isopoda and Isoptera. This was possibly due to the shortage of plants as shelter and the lack of organic matter as food. One area (site H), with a high level of landfill gas in the soil zone, had a lower diversity of soil animals than another area (site L) with a lower level of landfill gas. Some edaphic factors such as moisture content and concentrations of K, Na and Mg in the “contaminated” site H may also have resulted in lower numbers of species and individuals.     

Increasing biogas production from sewage sludge anaerobic co-digestion process by adding crude glycerol from biodiesel industry

In an effort to convert waste streams to energy in a green process, glycerol from biodiesel manufacturing has been used to increase the gas production and methane content of biogas within a mesophilic anaerobic co-digestion process using primary sewage sludge. Glycerol was systematically added to the primary digester from 0% to 60% of the organic loading rate (OLR). The optimum glycerol loading range was from 25% to 60% OLR. This resulted in an 82–280% improvement in specific gas production. Following the feeding schedule described, the digesters remained balanced and healthy until inhibition was achieved at 70% glycerol OLR. This suggests that high glycerol loadings are possible if slow additions are upheld in order to allow the bacterial community to adjust properly. Waste water treatment plant operators with anaerobic digesters can use the data to increase loadings and boost biogas production to enhance energy conversion. This process provides a safe, environmentally friendly method to convert a typical waste stream to an energy stream of biogas.     

旋转填充床分离沼气中的CO_2

以水为吸收液,采用旋转填充床分离微生物厌氧发酵沼气中的CO_2,考察了工艺条件对CO_2吸收效果的影响。实验结果表明:进液量越大、气液比越小、进口CO_2体积分数越小、操作压力越大、进液温度越低则CO_2的吸收效果越好,而床转速以适中为宜;在进液量60 L/h、气液比3.3、床转速1 000 r/min、进口CO_2体积分数40%、操作压力1.2 MPa、进液温度5℃的条件下,CO_2吸收率为57.4%,提纯后气体的CO_2体积分数为17%。