Biodesulfurization of landfill biogas by a pilot-scale bioscrubber: Operational limits and microbial analysis.

Biogas serves as a crucial renewable energy vector to ensure a more sustainable energy future. However, the presence of hydrogen sulfide (H2S) limits its application in various sectors, emphasizing the importance of effective H2S removal techniques for maximizing its potential. In the present study, the limits of a pilot-scale bioscrubber for biogas desulfurization was study in a real scenario. An increase in the superficial liquid velocity resulted in significant improvements in the H2S removal efficiency, increasing from 76 ± 8% (elimination capacity of 6.2 ± 0.5 gS-H2S m-3 h-1) to 97.7 ± 0.5% (elimination capacity of 8 ± 1 gS-H2S m-3 h-1) as the superficial liquid velocity increased from 50 ± 3 m h-1 to 200 ± 8 m h-1. A USL of 161.4 ± 0.5 m h-1 was able to achieve outlet H2S concentrations as low as 3 ± 1 ppmv (H2S removal efficiency of 97 ± 1%) for 7 days. High superficial liquid velocity favoured the aerobic H2S oxidation reducing the nitrate demand. The maximum EC reached throughout the operation was 50.8 ± 0.6 gS-H2S m-3 h-1 (H2S removal efficiency of 96 ± 1%) and a sulfur production of 60%. Studies in batch flocculation experiments showed sulfur removal rates up to 97.6 ± 0.9% with a cationic flocculant dose of 75 mg L-1. Microbial analysis revealed that the predominant genus with sulfo-oxidant capacity during periods of low H2S inlet load was Thioalkalispira-sulfurivermis (61-69%), while in periods of higher H2S inlet load, family Arcobacteraceae was the most prevalent (11%).

Assessing main process mechanism and rates of sulfate reduction by granular biomass fed with glycerol under sulfidogenic conditions.

Sulfate-reducing bioreactors for sulfide production are the initial stage of processes targeting elemental sulfur recovery from sulfate-rich effluents. In this work, the principal reactions involved in glycerol fermentation and sulfate reduction using glycerol and its fermentation products as electron donors were assessed together with their specific consumption/production rates. A battery of batch activity tests with and without sulfate were performed with glycerol and with each fermentation product using a non-methanogenic but sulfidogenic granular sludge from an up-flow anaerobic sludge blanket (UASB) reactor operated under long-term while fed with crude glycerol. As a result, a mechanistic approach based on the experimental observations is proposed in this work. Glycerol was mainly fermented to 1,3-propanediol, ethanol, formate, propionate and acetate by fermentative bacteria. All organic intermediates were found to be further used by sulfate reducing bacteria (SRB) for sulfate reduction except for acetate. The most abundant genus detected under sulfidogenic conditions were Propionispora (15.2%), Dysgonomonas (13.2%), Desulfobulbus (11.6%) and Desulfovibrio (10.8%). The last two SRB genera accounted for 22.4% of the total amount of retrieved sequences, which were probably performing an incomplete oxidation of the carbon source in the sulfidogenic UASB reactor. As single substrates, specific sulfate reduction rates (SRRs) using low molecular weight (MW) carbon sources (formate and ethanol) were 39% higher than those using high-MW ones (propionate, 1,3-propanediol and butanol). However, SRRs in glycerol-fed tests showed that 1,3-propanediol played a major role in sulfate reduction in addition to formate and ethanol.

Feasibility of S-rich streams valorization through a two-step biosulfur production process.

A bioscrubbing process named SONOVA has been developed, tested and assessed herein to valorize flue gases containing SOx. The process consists in a first scrubbing stage, to absorb and oxidize SO2 to sulfate, followed by a two-step biological stage. It consists of (1) an up-flow anaerobic sludge (UASB) reactor to reduce sulfate to sulfide with crude glycerol and (2) a continuous stirred tank reactor (CSTR) to partially oxidize sulfide to elemental sulfur (S0). SONOVA integrates the reutilization of resources, using the effluent of the biological stage as a sorbent agent and the residual heat of flue gases to dry the product. S0 is then obtained as a value-added product, which nowadays is produced from fossil fuels. In this research, SO2 concentrations up to 4000 ppmv were absorbed in 2 s of gas contact time in the spray-scrubber with removal efficiencies above 80%. The UASB reduced up to 9.3 kg S-Sulfate m-3 d-1 with sulfide productivities of 6 kg S m-3 d-1 at an hydraulic retention time (HRT) as low as 2 h. Finally, CSTR was fed with the UASB effluent and operated at HRT ranging from 12 h to 4 h without biomass wash-out. Sulfide was fully oxidized to S0 with a productivity of 2.3 kg S m-3 d-1 at the lowest HRT tested. Overall, this research has explored not only maximum capabilities of each SONOVA stage but has also assessed the interactions between the different units, which opens up the possibility of recovering S0 from harmful SOx emissions, optimizing resources utilization and costs.

Interaction between sorption and biodegradation in a biofilter packed with activated carbon.

The main objective of this study is to evaluate qualitatively and quantitatively the effect of starvation periods in the biodegradation capacity of microorganisms when the support media is a material with high sorption capacity. Pollutant sorption and biodegradation, which occur simultaneously in the biofilter, describe the overall behavior of the air treatment system during normal operation and during starvation periods. Results obtained in the present study demonstrate that sorption capacity of the material not only plays an important role during the start-up of operation, but it is also important during steady operation. Simultaneously, as biomass grows on the support, biodegradation becomes more decisive in the performance. It was found that zones of packing material with low moisture content are controlled by the sorption mechanism, at the expense of biodegradation, and they are essential as a pollutant reservoir during starvation periods. In the present study a significant decrease in the biodegradation capacity of microorganisms immobilized on activated carbon was not observed as a consequence of continuous load interruptions.

Bacterial community analysis of a gas-phase biotrickling filter for biogas mimics desulfurization through the rRNA approach.

The bacterial composition of a lab-scale biotrickling filter (BTF) treating high loads of H(2)S was investigated by the rRNA approach. Two 16S rRNA gene clone libraries were established 42 and 189 d after reactor startup, while fluorescent in-situ hybridization (FISH) with DNA probes was performed throughout 260d of reactor operation. Diversity, community structure and metamorphosis were studied from reactor startup to fully-established pseudo-steady state operation at near neutral pH and at an inlet H(2)S concentration of 2000 ppmv (load of 55.6g H(2)S m(-3)h(-1)). In addition, FISH was used for assessing the spatial distribution of sulfur-oxidizing bacteria (SOB) along the length of the reactor under pseudo-steady state operation. A major shift in the diversity of the community was observed with the operating time, from a well-diverse community at startup to pseudo-steady state operation with a majority of retrieved sequences affiliated to SOB of the sulfur cycle including Thiothrix spp., Thiobacillus spp., and Sulfurimonas denitrificans. Although aerobic species were predominant along the BTF, a vertical stratification was encountered, in which facultative anaerobes had a major relative abundance in the inlet part of the BTF, where the sulfide to oxygen ratio was higher. The observed changes were related to the trophic properties of the community, the DO concentration, the accumulation of elemental sulfur and the operation at neutral pH.

A comparative study based on physical characteristics of suitable packing materials in biofiltration.

In the present work, 10 packing materials commonly used as support media in biofiltration are analysed and compared to evaluate their suitability according to physical characteristics. The nature of the packing material in biofilters is an important factor for the success in their construction and operation. Different packing materials have been used in biofiltration without a global agreement about which ones are the most adequate for biofiltration success. The materials studied were chosen according to previous works in the field of biofiltration including both organic and inorganic (or synthetic) materials. A set of nine different parameters were selected to cope with well-established factors, such as a material-specific surface area, pressure drop, nutrient supply, water retentivity, sorption capacity, and purchase cost. One ranking of packing materials was established for each parameter studied in order to define a relative suitability degree. Since biofiltration success generally depends on a combination of the ranked parameters, a procedure was defined to compare packing materials suitability under common situations in biofiltration. The selected scenarios, such as biofiltration of intermittent loads of pollutants and biofiltration of waste gases with low relative humidity, were investigated. The results indicate that, out of the packing materials studied, activated carbons were ranked top of several parameter rankings and were shown to be a significantly better packing material when parameters were combined to assess such selected scenarios.

Oxidation by Fenton's reagent combined with biological treatment applied to a creosote-comtaminated soil.

In this study, we investigated the feasibility of using Fenton oxidation to remove sorbed polycyclic aromatic hydrocarbons (PAHs) in aged soil samples with creosote oil from a wood preserving site. The optimal dosage of reagents was determined by a statistical method, the central composite rotatable experimental design. The maximum PAH removal was 80% with a molar ratio of oxidant/catalyst equal to 90:1. In general low molecular weight PAHs (3 rings) were degraded more efficiently than higher molecular weight PAHs (4 and 5 rings). The hydrogen peroxide decomposition kinetic was studied in the presence of KH(2)PO(4) as stabilizer. The kinetic data were fitted to a simple model, the pseudo-first-order which describes the hydrogen peroxide decomposition. The PAH kinetic degradation was also studied, and demonstrated that non-stabilized hydrogen peroxide was consumed in less than 30 min, whilst PAH removal continued for up to 24h. In a second part of the work, a combined chemical and biological treatment of the soil was carried out and shown to be dependent on the pre-oxidation step. Different reagent doses (H(2)O(2):Fe) were used (10, 20, 40, 60:1) in the pre-treatment step. An excess of hydrogen peroxide resulted in a poor biological removal, thus the optimal molar ratio of H(2)O(2):Fe for the combined process was 20:1. The combined treatment resulted in a maximum total PAH removal of 75% with a 30% increase in removal due to the biodegradation step. The sample with highest PAH removal in the pre-oxidation step led to no further increase in removal by biological treatment. This suggests that the more aggressive chemical pre-oxidation does not favour biological treatment. The physico-chemical properties of the pollutants were an important factor in the PAH removal as they influenced chemical, biological and combined treatments.

Sorption kinetics of polycyclic aromatic hydrocarbons removal using granular activated carbon: intraparticle diffusion coefficients.

Granular activated carbon (GAC) was evaluated as a suitable sorbent for polycyclic aromatic hydrocarbons (PAHs) removal from aqueous solutions. For this purpose, kinetic measurements on the extraction of a family of six PAHs were taken. A morphology study was performed by means of a scanning electron microscopy (SEM) analysis of GAC samples. Analyses of the batch rate data for each PAH were carried out using two kinetic models: the homogenous particle diffusion model (HPDM) and the shell progressive model (SPM). The process was controlled by diffusion rate the solutes (PAHs) that penetrated the reacted layer at PAH concentrations in the range of 0.2-10 mg L(-1). The effective particle diffusion coefficients (D(eff)) derived from the two models were determined from the batch rate data. The Weber and Morris intraparticle diffusion model made a double contribution to the surface and pore diffusivities in the sorption process. The D(eff) values derived from both the HPMD and SPM equations varied from 1.1 x 10(-13) to 6.0 x 10(-14) m(2) s(-1). The simplest model, the pore diffusion model, was applied first for data analysis. The model of the next level of complexity, the surface diffusion model, was applied in order to gain a deeper understanding of the diffusion process. This model is able to explain the data, and the apparent surface diffusivities are in the same order of magnitude as the values for the sorption of functionalized aromatic hydrocarbons (phenols and sulphonates) that are described in the literature.

Kinetics of sorption of polyaromatic hydrocarbons onto granular activated carbon and Macronet hyper-cross-linked polymers (MN200).

Polymeric supports are presented as an alternative to granular activated carbon (GAC) for organic contaminant removal from groundwater using permeable reactive barriers (PRB). The search for suitable polymeric sorbents for hydrocarbon extraction from aqueous streams has prompted the synthesis of new resins incorporating new functionalities or modifying the polymer network properties that solve many of the existing problems. Between them, the new type of polymeric sorbents Macronet Hypersol containing a styrene-divinylbenzene macroporous hyperreticulated network has been evaluated. Because of their potential sorptive properties, tests were conducted to determine the feasibility of using them as a low-cost reactive material for groundwater applications. The present work describes the sorption of six polycyclic hydrocarbons (PAHs) from aqueous solution onto both Macronet polymeric sorbent MN200 and granular activated carbon. Batch experiments were performed to determine loading rates of a family of PAHs (naphthalene, fluorene, anthracene, acenaphthene, pyrene, and fluoranthene), from a simple two-rings PAH (naphthalene) up to a four-ring PAH (pyrene). The behavior of a non-functionalized Macronet support (MN200) was compared with the behavior of a recognized material, granular activated carbon (GAC). Analyses of the respective rate data with three theoretical models (pseudo-first- and pseudo-second-order reaction models and the Elovich model) were used to describe the PAH sorption kinetics. Sorption rate constants were determined by graphical analysis of the proposed models. The study showed that sorption systems followed a pseudo-first-order reaction model, although the pseudo-second-order reaction model provides an acceptable description of the sorption process. Graphical analysis showed that the sorption process with activated carbon is a more complex process than the one observed for hyper-cross-linked polymers (MN200). A simulation of the barrier thickness needed to treat a PAH-polluted plume showed that 0.1-1 m of sorption media is enough even for high water fluxes such as 0.1-2 m(3)/m(2)/day for both sorbents.