Sulfur Toxicity and Media Capacity for H2S Removal in Biofilters Packed with a Natural or a Commercial Granular Medium

Abstract

Two types of media, a natural medium (wood chips) and a commercially engineered medium, were evaluated for sulfur inhibition and capacity for removal of hydrogen sulfide (H₂S). Sulfate was added artificially (40, 65, and 100 mg of S/g of medium) to test its effect on removal efficiency and the media. A humidified gas stream of 50 ppm by volume H₂S was passed through the media-packed columns, and effluent readings for H₂S at the outlet were measured continuously. The overall H₂S baseline removal efficiencies of the column packed with natural medium remained >95% over a 2-day period even with the accumulated sulfur species. Added sulfate at a concentration high enough to saturate the biofilter moisture phase did not appear to affect the H₂S removal process efficiency. The results of additional experiments with a commercial granular medium also demonstrated that the accumulation of amounts of sulfate sufficient enough to saturate the moisture phase of the medium did not have a significant effect on H₂S removal.

When the pH of the biofilter medium was lowered to 4, H₂S removal efficiency did drop to 36%. This work suggests that sulfate mass transfer through the moisture phase to the biofilm phase does not appear to inhibit H₂S removal rates in biofilters. Thus, performance degradation for odor-removing biofilters or H₂S breakthrough in field applications is probably caused by other consequences of high H₂S loading, such as sulfur precipitation.     

Changes in physical properties of a compost biofilter treating hydrogen sulfide

A technique is presented that can be used to estimate the changes in physical structure in a natural biofilter packing medium, such as compost, over time. The technique applies information from tracer studies, grain size distribution, and pressure drop analysis to a model that estimates the number of channels, average channel diameter, number of particles, and specific surface area of the medium. Important operational factors, such as moisture content, pressure drop, and sulfate accumulation also were evaluated both in a conventionally operated biofilter and in one operated with periodic compost mixing. In the conventionally operated laboratory-scale compost biofilter, hydrogen sulfide (H2S) removal efficiency decreased from 100% to approximately 90% over 206 days of operation. In a similar system, operated with compost mixing, the H2S removal efficiency was maintained near 100%. Variations in media moisture conditions and specific surface area can explain the results observed in this study. Under conventional operation, drying near the inlet disintegrated the compost particles, producing a large number of particles and flow channels and increasing the specific surface area. At the top of the column, where moisture was added, particle size increased and specific surface area decreased. In the column with media mixing, moisture content, particle size, and specific surface area remained homogeneous.     

Reusing H2S-exhausted carbon as packing material for odor biofiltration

Exhausted carbon coming from the H2S adsorption process is a big environmental problem in Wastewater Treatment Plants. In this study, reusing exhausted carbon as a carrier of sulfide-oxidizing bacteria in lab-scale biofilters was evaluated. The exhausted carbons from different heights of the adsorption bed have different exhaustion extents, i.e. characteristics in terms of sulfur content, pH and porosity. Therefore, four biofilters were packed separately with exhausted carbon from top, middle, bottom of H2S adsorption bed, and a mixture of the three, to investigate the suitability for further H2S biofiltration. The results showed a quick startup in these biofilters (approximately 80 h). The numbers of sulfide-oxidizing bacteria immobilized on activated carbon were approximately 4.8, 9.2 and 14 x 108 CFU g-1 top, middle and bottom carbon after the 240-h operation, respectively. In addition, the biofilters demonstrated a rapid recovery to the original removal efficiency (RE) within 2 h after the H2S spike loadings. After a 110-h shutdown, the RE was rapidly recovered for all the biofilters within 5 h, with a shorter time (1 h) observed for the bottom carbon biofilter. The H2S removal mechanism of these biofilters was studied through a full analysis of sulfur products in both liquid (recycling medium) and activated carbon, and variable characterization of activated carbon before and after biofiltration. This study shows that the exhausted carbon-based biofilter is a feasible and economical alternative to conventional odor biofiltration.     

Full-scale biofilter reduction efficiencies assessed using portable 24-hour sampling units

Portable 24-hr sampling units were used to collect air samples from eight biofilters on four animal feeding operations. The biofilters were located on a dairy, a swine nursery, and two swine finishing farms. Biofilter media characteristics (age, porosity, density, particle size, water absorption capacity, pressure drop) and ammonia (NH3), hydrogen sulfide (H2S), sulfur dioxide (SO2), methane (CH4), and nitrous oxide (N2O) reduction efficiencies of the biofilters were assessed. The deep bed biofilters at the dairy farm, which were in use for a few months, had the most porous media and lowest unit pressure drops. The average media porosity and density were 75% and 180 kg/m3, respectively. Reduction efficiencies of H2S and NH3 (biofilter 1: 64% NH3, 76% H2S; biofilter 2: 53% NH3, 85% H2S) were close to those reported for pilot-scale biofilters. No N2O production was measured at the dairy farm. The highest H2S, SO2, NH3, and CH4 reduction efficiencies were measured from a flat-bed biofilter at the swine nursery farm. However, the highest N2O generation (29.2%) was also measured from this biofilter. This flat-bed biofilter media was dense and had the lowest porosity. A garden sprinkler was used to add water to this biofilter, which may have filled media pores and caused N2O production under anaerobic conditions. Concentrations of H2S and NH3 were determined using the portable 24-hr sampling units and compared to ones measured with a semicontinuous gas sampling system at one farm. Flat-bed biofilters at the swine finishing farms also produced low amounts of N2O. The N2O production rate of the newer media (2 years old) with higher porosity was lower than that of older media (3 years old) (P = 0.042).     

Two-stage biofilter for effective NH3 removal from waste gases containing high concentrations of H2S

A high H2S concentration inhibits nitrification when H2S and NH3 are simultaneously treated in a single biofilter. To improve NH3 removal from waste gases containing concentrated H2S, a two-stage biofilter was designed to solve the problem. In this study, the first biofilter, inoculated with Thiobacillus thioparus, was intended mainly to remove H2S and to reduce the effect of H2S concentration on nitrification in the second biofilter, and the second biofilter, inoculated with Nitrosomonas europaea, was to remove NH3. Extensive studies, which took into account the characteristics of gas removal, the engineering properties of the two biofilters, and biological parameters, were conducted in a 210-day operation. The results showed that an average 98% removal efficiency for H2S and a 100% removal efficiency for NH3 (empty bed retention time = 23-180 sec) were achieved after 70 days. The maximum degradation rate for NH3 was measured as 2.35 g N day(-1) kg of dry granular activated carbon(-1). Inhibition of nitrification was not found in the biofilter. This two-stage biofilter also exhibited good adaptability to shock loading and shutdown periods. Analysis of metabolic product and observation of the bacterial community revealed no obvious acidification or alkalinity phenomena. In addition, a lower moisture content (approximately 40%) for microbial survival and low pressure drop (average 24.39 mm H2O m(-1)) for system operation demonstrated that the two-stage biofilter was energy saving and economic. Thus, the two-stage biofilter is a feasible system to enhance NH3 removal in the concentrated coexistence of H2S.     

Design and performance characterization strategy using modeling for biofiltration control of odorous hydrogen sulfide

Biofilter, dynamic modeling software characterizing contaminant removal via biofiltration, was used in the preliminary design of a biofilter to treat odorous hydrogen sulfide (H2S). Steady-state model simulations were run to generate performance plots for various influent concentrations, loadings, residence times, media sizes, and temperatures. Although elimination capacity and removal efficiency frequently are used to characterize biofilter performance, effluent concentration can be used to characterize performance when treating to a target effluent concentration. Model simulations illustrate that, at a given temperature, a biofilter cannot reduce H2S emissions below a minimum value, no matter how large the biofilter or how long the residence time. However, a higher biofilter temperature results in lower effluent H2S concentrations. Because dynamic model simulations show that shock loading can significantly increase the effluent concentration above values predicted by the steady-state model simulations, it is recommended that, to consistently meet treatment objectives, dynamic feed conditions should be considered. This study illustrates that modeling can serve as a valuable tool in the design and performance optimization of biofilters.     

Biogeochemical analysis of hydrogen sulfide removal by a lava-rock packed biofilter.

Although lava-rock-based biofilters have demonstrated their efficiencies for hydrogen sulfide (H2S) removal found in odorous air emissions, the biogeochemical basis for this removal is unclear. In this study, samples of lava rock and rinse water from biofilters at Cedar Rapids Water Pollution Control Facilities (Iowa) were used to study the structure and chemical composition of lava rock and to identify the predominant microorganism(s) present in lava-rock-based biofilters. It was found that iron, in the form of Fe2+ and Fe3+, was present in lava rock. Although literature suggests that Acidithiobacillus thiooxidans are primarily responsible for gaseous H2S removal in biofilters, our study showed that Acidithiobacillus ferrooxidans was the dominant microorganism in the lava-rock-based biofilters. A novel mechanism for H2S removal in a lava-rock-based biofilter is proposed based on the biogeochemical analysis of lava rock.     

Ethylbenzene removal in a multiple-stage biofilter

In practice, biofilters are often conceived as entire, single-unit systems. However, the activity of a biofilter varies greatly over its depth. For a given period, each stage of the biofilter dominates ethylbenzene removal. Ethylbenzene was continuously removed in a mixed-medium biofilter. The overall removal efficiency of the ethylbenzene ranged from 70% to greater than 99%. In the upflow biofilter, the most dominant ethylbenzene degrading stage shifted consecutively from the bottom to the top of the reactor. Average water content throughout the biofilter media was relatively consistent. However, the water content of each stage fluctuated dramatically and was correlated with the ethylbenzene removal rate. Without any water addition, the biofilter was operated for 62 days above the target removal efficiency of 80%. A 9-month slow-release fertilizer, mixed with composting media, was an effective way to eliminate the nutrient deficiency in the biofilter operation.     

Ethylbenzene Removal in a Multiple-Stage Biofilter

ABSTRACT

In practice, biofilters are often conceived as entire, single-unit systems. However, the activity of a biofilter varies greatly over its depth. For a given period, each stage of the biofilter dominates ethylbenzene removal. Ethylbenzene was continuously removed in a mixed-medium biofilter. The overall removal efficiency of the ethylbenzene ranged from 70% to greater than 99%. In the upflow biofilter, the most dominant ethylbenzene degrading stage shifted consecutively from the bottom to the top of the reactor. Average water content throughout the biofilter media was relatively consistent. However, the water content of each stage fluctuated dramatically and was correlated with the ethylbenzene removal rate. Without any water addition, the biofilter was operated for 62 days above the target removal efficiency of 80%. A 9-month slow-release fertilizer, mixed with composting media, was an effective way to eliminate the nutrient deficiency in the biofilter operation.     

Carbon disulfide and hydrogen sulfide removal with a peat biofilter

Simultaneous removal of H2S and CS2 was studied with a peat biofilter inoculated with a Thiobacillus strain that oxidizes both compounds in an acidic environment. Both sulfurous gases at concentrations below 600 mg S/m3 were efficiently removed, and the removal efficiencies were similar, 99%, with an empty bed retention time (EBRT) of more than 60 sec. Concentrations greater than 1300-5000 mg S/m3 caused overloading of the filter material, resulting in high H2SO4 production, accumulation of elemental sulfur, and reduced removal efficiency. The highest sulfur removal rate achieved was 4500 g-S/day/m3 filter material. These results indicate that peat is suitable as a biofilter material for the removal of a mixture of H2S and CS2 when concentrations of gases to be purified are low (less than 600 mg/m3), but it is still odorous and toxic to the environment and humans.     

Kinetic evaluation of H2S and NH3 biofiltration for two media used for wastewater lift station emissions

In this study, biofiltration using a natural wood chip medium and a commercial biofiltration medium was evaluated for the removal of moderate concentrations of hydrogen sulfide (H2S) (up to 100 parts per million by volume [ppmv]) in the presence of significant concentrations of ammonia (NH3). These levels were chosen as representative of wastewater lift station emissions in the Brownsville, TX, area. NH3-removing portions of the biofilms may compete with H2S-removing portions and inhibit H2S removal. H2S process removal efficiencies for the commercial and natural media ranged from 90 to 96% depending on inlet loading and media type and bed height. Kinetic analysis of the H2S removal process followed apparent first-order reaction behavior. The average first-order reaction rates were 0.03 sec(-1) for the commercial medium and 0.09 sec(-1) for the natural medium. Pressure drops across the columns ranged from 0.41 in. H2O/ft for the commercial medium to 1.41 in. H2O/ft for the natural medium. NH3 gas levels of up to 80 ppmv did not affect the H2S removal process efficiency, and calculated kinetic rate constants for H2S removal remained almost the same. The NH3 gas also was removed simultaneously with the H2S up to 98% removal efficiency by the commercial medium.     

Development and performance of an alternative biofilter system

Step tracer tests were carried out on lab-scale biofilters to determine the residence time distributions (RTDs) of gases passing through two types of biofilters: a standard biofilter with vertical gas flow and a modified biofilter with horizontal gas flow. Results were used to define the flow patterns in the reactors. "Non-ideal flow" indicates that the flow reactors did not behave like either type of ideal reactor: the perfectly stirred reactor [often called a "continuously stirred tank reactor" (CSTR)] or the plug-flow reactor. The horizontal biofilter with back-mixing was able to accommodate a shorter residence time without the usual requirement of greater biofilter surface area for increased biofiltration efficiency. Experimental results indicated that the first bed of the modified biofilter behaved like two CSTRs in series, while the second bed may be represented by two or three CSTRs in series. Because of the flow baffles used in the horizontal biofilter system, its performance was more similar to completely mixed systems, and hence, it could not be modeled as a plug-flow reactor. For the standard biofilter, the number of CSTRs was found to be between 2 and 9 depending on the airflow rate. In terms of NH3 removal efficiency and elimination capacity, the standard biofilter was not as good as the modified system; moreover, the second bed of the modified biofilter exhibited greater removal efficiency than the first bed. The elimination rate increased as biofilter load increased. An opposite trend was exhibited with respect to removal efficiency.     

Control of Organic Emissions from Surface Coating Operations

ABSTRACT

Step tracer tests were carried out on lab-scale biofilters to determine the residence time distributions (RTDs) of gases passing through two types of biofilters: a standard biofilter with vertical gas flow and a modified biofilter with horizontal gas flow. Results were used to define the flow patterns in the reactors. “Non-ideal flow” indicates that the flow reactors did not behave like either type of ideal reactor: the perfectly stirred reactor [often called a "continuously stirred tank reactor" (CSTR)] or the plug-flow reactor.

The horizontal biofilter with back-mixing was able to accommodate a shorter residence time without the usual requirement of greater biofilter surface area for increased biofiltration efficiency. Experimental results indicated that the first bed of the modified biofilter behaved like two CSTRs in series, while the second bed may be represented by two or three CSTRs in series. Because of the flow baffles used in the horizontal biofilter system, its performance was more similar to completely mixed systems, and hence, it could not be modeled as a plug-flow reactor. For the standard biofilter, the number of CSTRs was found to be between 2 and 9 depending on the airflow rate. In terms of NH₃ removal efficiency and elimination capacity, the standard biofilter was not as good as the modified system; moreover, the second bed of the modified biofilter exhibited greater removal efficiency than the first bed. The elimination rate increased as biofilter load increased. An opposite trend was exhibited with respect to removal efficiency.     

Long-term operation of a biofilter for simultaneous removal of H2S and NH3

Simultaneous removal of NH3 and H2S was investigated using two types of biofilters--one packed with wood chips and the other with granular activated carbon (GAC). Experimental tests and measurements included analyses of removal efficiency (RE), metabolic products, and results of long-term operation (around 240 days). The REs for NH3 and H2S were 92 and 99.9%, respectively, before deactivation. After deactivation, the RE for NH3 and H2S were decreased to 30-50% and 75%, respectively. The activity of nitrifying bacteria was inhibited by high concentrations of H2S (over 200 ppm) but recovered gradually after H2S addition was ceased. However, the Thiobacillus thioparus as sulfur oxidizing bacteria did not show inhibition at the NH3 concentration under 150-ppm conditions. The deactivation of the biofilter was caused by metabolic products [elemental sulfur and (NH4)2SO4] accumulating on the packing materials during the extended operation. The removal capacities for NH3 and H2S were 6.0-8.0 and 45-75 mg N, S/L/hr, respectively.     

H₂S abatement in a biotrickling filter using iron(III) foam media

Airstreams polluted with H(2)S at inlet loads ranging from 2.4 to 40.9 g H(2)Sm(-3)h(-1) were treated in a biotrickling reactor packed with hematite bearing, open pore foam units, at Empty Bed Residence Times (EBRT) ranging from 20 to 60s over a period of 80 d, with almost complete removal of the pollutant from the startup of the system. The media had been seeded with sludge from a local water works facility, and removal efficiencies in excess of 80% were consistently observed along the operation of the reactor, with an average of 98%. Based on section performance, being a section one third of the bed length, observed elimination capacities (EC) reached up to 88.7 g H(2)Sm(-3)h(-)(1) and 72.0 g H(2)Sm(-3)h(-1) at section EBRT of 10 and 7s, respectively. The observed EC values compared much better than data reported on other packed bed reactors using biological iron oxidization to treat H(2)S airstreams indirectly, and so did it when comparing the EC per unit of specific area in a similar study using polyurethane (PU) foams. Further, and unlike PU packed biofilters, no compaction occurred due to the iron foam rigidity, which translated in much better observed gas phase pressure drop as opposed to other conventional biofilters. Denaturing gel gradient electrophoresis was performed on the biomass collected in the packing after the biofilter service, and it was found that though a multi bacterial colony was seeded in the system via the sludge, the only surviving genus was the iron oxidizing Alicyclobacillus spp.     

A comparative study in treating two VOC mixtures in trickle bed air biofilters

Two independent parallel trickling bed air biofilters (TBABs) ("A" and "B") with two different typical VOC mixtures were investigated. Toluene, styrene, methyl ethyl ketone (MEK), and methyl isobutyl ketone (MIBK) were the target VOCs in the mixtures. Biofilter "A" was fed equal molar ratio of the VOCs and biofilter "B" was fed a mixture based on EPA 2003 emission report. Backwashing and substrate starvation operation were conducted as biomass control. Biofilter "A" and "B" maintained 99% overall removal efficiency for influent concentration up to 500 and 300 ppmv under backwashing operating condition, respectively. The starvation study indicated that it can be an effective biomass control for influent concentrations up to 250 ppmv for biofilter "A" and 300 ppmv for "B". Re-acclimation of biofilter performance was delayed with increase of influent concentration for both biofilters. Starvation operation helped the biofilter to recover at low concentrations and delayed re-acclimation at high concentrations. Furthermore, re-acclamation for biofilter "B" was delayed due to its high toluene content as compared to biofilter "A". The pseudo first-order removal rate constant decreased with increase of volumetric loading rate for both biofilters. MEK and MIBK were completely removed in the upper 3/8 media depth. While biofilter depth utilization for the removal of styrene and toluene increased with increase of influent concentrations for both biofilters. However, toluene removal utilized more biofilter depth for biofilter "B" as compared to biofilter "A".     

Design and Performance Characterization Strategy Using Modeling for Biofiltration Control of Odorous Hydrogen Sulfide

Abstract

Biofilter, dynamic modeling software characterizing contaminant removal via biofiltration, was used in the preliminary design of a biofilter to treat odorous hydrogen sulfide (H₂S). Steady-state model simulations were run to generate performance plots for various influent concentrations, loadings, residence times, media sizes, and temperatures. Although elimination capacity and removal efficiency frequently are used to characterize biofilter performance, effluent concentration can be used to characterize performance when treating to a target effluent concentration. Model simulations illustrate that, at a given temperature, a biofilter cannot reduce H₂S emissions below a minimum value, no matter how large the biofilter or how long the residence time. However, a higher biofilter temperature results in lower effluent H₂S concentrations. Because dynamic model simulations show that shock loading can significantly increase the effluent concentration above values predicted by the steady-state model simulations, it is recommended that, to consistently meet treatment objectives, dynamic feed conditions should be considered. This study illustrates that modeling can serve as a valuable tool in the design and performance optimization of biofilters.     

Removal of low concentrations of carbon tetrachloride in compost-based biofilters operated under methanogenic conditions.

Research was performed to demonstrate the removal of carbon tetrachloride (CT) using compost biofilters operated under methanogenic conditions. Biofilters were operated at an empty-bed residence time of 2.8 minutes using nitrogen as the atmosphere. Hydrogen and carbon dioxide were supplied as an electron donor and carbon source, respectively, during acclimation of the bed medium microbes. Once methanogenesis was demonstrated, CT flow to the biofilter was established. Biofilters were operated over a CT concentration range from 20 to 700 ppbv for 6 months. Bed medium microbes were able to remove up to 75% of the inlet CT. At excessively high CT concentrations (> 500 ppmv), methane production and hydrogen utilization by the bed medium microbes appeared to be inhibited. CT removal by the biofilter decreased when the hydrogen supply was removed from the biofilter inlet, indicating that hydrogen acted as the electron donor for reductive dechlorination. The removal efficiency and relatively low empty bed residence times demonstrated by these laboratory-scale biofilters indicate that anaerobic biofiltration of CT may be a feasible full-scale process.     

Effects of biofilter media depth and moisture content on removal of gases from a swine barn

Media depth (MD) and moisture content (MC) are two important factors that greatly influence biofilter performance. The purpose of this study was to investigate the combined effect of MC and MD on removing ammonia (NH₃), hydrogen sulfide (H₂S), and nitrous oxide (N₂O) from swine barns. Biofiltration performance of different MDs and MCs in combination based on a mixed medium of wood chips and compost was monitored. A 3 × 3 factorial design was adopted, which included three levels of the two factors (MC: 45%, 55%, and 67% [wet basis]; MD: 0.17, 0.33, and 0.50 m). Results indicated that high MC and MD could improve NH₃ removal efficiency, but increase outlet N₂O concentration. When MC was 67%, the average NH₃ removal efficiency of three MDs (0.17, 0.33, and, 0.50 m) ranged from 77.4% to 78.7%; the range of average H₂S removal efficiency dropped from 68.1–90.0% (1–34 days of the test period) to 36.8–63.7% (35–58 days of the test period); and the average outlet N₂O concentration increased by 25.5–60.1%. When MC was 55%, the average removal efficiency of NH₃, H₂S, and N₂O for treatment with 0.33 m MD was 72.8 ± 5.9%, 70.9 ± 13.3%, and –18.9 ± 8.1%, respectively; and the average removal efficiency of NH₃, H₂S, and N₂O for treatment with 0.50 m MD was 77.7 ± 4.2%, 65.8 ± 13.7%, and –24.5 ±12.1%, respectively. When MC was 45%, the highest average NH₃ reduction efficiency among three MDs was 60.7% for 0.5 m MD, and the average N₂O removal efficiency for three MDs ranged from –18.8% to –12.7%. In addition, the pressure drop of 0.33 m MD was significantly lower than that of 0.50 m MD (p < 0.05). To obtain high mitigation of NH₃ and H₂S and avoid elevated emission of N₂O and large pressure drop, 0.33 m MD at 55% MC is recommended.

Implications: The performances of biofilters with three different media depths (0.17, 0.33, and 0.50 m) and three different media moisture contents (45%, 55%, and 67% [wet basis]) were compared to remove gases from a swine barn. Using wood chips and compost mixture as the biofilters media, the combination of 0.33 m media depth and 55% media moisture content is recommended to obtain good reduction of NH₃ and H₂S, and to simultaneously prevent elevated emission of N₂O and large pressure drop across the media.     

Long-Term Operation of a Biofilter for Simultaneous Removal of H2S and NH3

Abstract

Simultaneous removal of NH₃ and H₂S was investigated using two types of biofilters—one packed with wood chips and the other with granular activated carbon (GAC). Experimental tests and measurements included analyses of removal efficiency (RE), metabolic products, and results of long-term operation (around 240 days). The REs for NH₃ and H₂S were 92 and 99.9%, respectively, before deactivation. After deactivation, the RE for NH₃ and H₂S were decreased to 30–50% and 75%, respectively. The activity of nitrifying bacteria was inhibited by high concentrations of H₂S (over 200 ppm) but recovered gradually after H₂S addition was ceased. However, the Thiobacillus thioparus as sulfur oxidizing bacteria did not show inhibition at the NH₃ concentration under 150-ppm conditions. The deactivation of the biofilter was caused by metabolic products [elemental sulfur and (NH₄)₂SO₄] ac-cumulating on the packing materials during the extended operation. The removal capacities for NH₃ and H₂S were 6.0–8.0 and 45–75 mg N, S/L/hr, respectively.