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.     

酸性洗涤塔-生物滤塔-生物曝气池组合工艺处理恶臭气体NH3和H2S

采用酸性洗涤塔、生物滤塔和生物曝气池的组合工艺处理NH3、H2S恶臭混合气体,研究表明,该组合工艺对NH3和H2S有很好的去除效果,在进气流量为35 L/min,喷淋量45 L/h时,NH3进气浓度50.15~525.4 mg/m3,H2S进气浓度10.23~110.36 mg/m3时,NH3单一进气去除率稳定在99%以上,H2S单一进气去除率90%以上。混合进气后,NH3去除率几乎为100%,H2S的去除率提高至98%以上。在一定的浓度范围内,NH3和H2S之间的相互作用对两者的去除效果没有明显的影响,而且起到了相互促进降解的作用。同时,进气流量和填料层高度都会影响NH3、H2S的去除率。系统对进气容积负荷变化的缓冲能力强,在偶尔超负荷条件下运行并不能使系统崩溃,并且微生物对高负荷逐渐表现出适应性。大部分溶于水的氨由生物曝气池去除,去除率达到96.9%。     

Absorption and Reaction Kinetics of Amines and Ammonia Solutions with Carbon Dioxide in Flue Gas

Abstract

The removal system for the absorption of CO₂ with amines and NH₃ is an advanced air pollution control device to reduce greenhouse gas emissions. Absorption of CO₂ by amines and NH₃ solutions was performed in this study to derive the reaction kinetics. The absorption of CO₂ as encountered in flue gases into aqueous solutions of monoethanolamine (MEA), diethanolamine (DEA), and NH₃ was carried out using a stirred vessel with a plane gas-liquid interface at 50 °C. Various operating parameters were tested to determine the effect of these variables on the absorption kinetics of the reactants in both gas and liquid phases and the effect of competitions between various reactants on the mass-transfer rate.

The observed absorption rate increases with increasing gas-liquid concentration, solvent concentration, temperature, and gas flow rate, but changes with the O₂ concentration and pH value. The absorption efficiency of MEA is better than that of NH₃ and DEA, but the absorption capacity of NH₃ is the best. The active energies of the MEA and NH₃ with CO₂ are 33.19 and 40.09 kJ/mol, respectively.     

Operational Characteristics of Effective Removal of H2S and NH3 Waste Gases by Activated Carbon Biofilter

Abstract

Simultaneous removal of hydrogen sulfide (H₂S) and am- gases. monia (NH₃) gases from gaseous streams was studied in a biofilter packed with granule activated carbon. Extensive studies, including the effects of carbon (C) source on the growth of inoculated microorganisms and gas removal efficiency, product analysis, bioaerosol emission, pressure drop, and cost evaluation, were conducted. The results indicated that molasses was a potential C source for inoculated cell growth that resulted in removal efficiencies of 99.5% for H₂S and 99.2% for NH₃. Microbial community observation by scanning electron microscopy indicated that granule activated carbon was an excellent support for microorganism attachment for long-term waste gas treatment. No disintegration or breakdown of biofilm was found when the system was operated for 140 days. The low bioaerosol concentration emitted from the biofilter showed that the system effectively avoided the environmental risk of bioaerosol emission. Also, the system is suitable to apply in the field because of its low pressure drop and treatment cost. Because NH₃ gas was mainly converted to organic nitrogen, and H₂S gas was converted to elemental sulfur, no acidification or alkalinity phenomena were found because of the metabolite products. Thus, the results of this study demonstrate that the biofilter is a feasible bioreactor in the removal of waste gases.     

Comments on “Relating Summer Ambient Particulate Sulfur,Sulfur Dioxide,and Light Scattering to Gaseous Tracer Emissions from the MOHAVE Power Project”

ABSTRACT

A trickle bed air biofilter (TBAB) was evaluated for the oxidation of NH₃ from an airstream. Six-millimeter Celite pellets (R-635) were used for the biological attachment medium. The efficiency of the biofilter in oxidizing NH₃ was evaluated using NH₃ loading rates as high as 48 mol NH₃/m³ hr and empty-bed residence times (EBRTs) as low as 1 min. Excess biomass was controlled through periodic backwashing of the biofilter with water at a rate sufficient to fluidize the medium. The main goal was to demonstrate that high removal efficiencies could be sustained over long periods of operation. Ammonia oxidation efficiencies in excess of 99% were consistently achieved when the pH of the liquid nutrient feed was maintained at 8.5. Quick recovery of the biofilter after backwashing was observed after only 20 min. Evaluation of biofilter performance with depth revealed that NH₃ did not persist in the gas phase beyond 0.3 m into the depth of the medium (26% of total medium depth).     

1988 APCA Government Agencies Directory

The biowaste fractions in municipal solid waste (MSW) are the main odor sources in landfill and cause widespread complaints from residents. The ammonia (NH₃) and hydrogen sulfide (H₂S) generation processes were simulated and compared between four typical biowaste fractions individually and combined in the mixed MSW. Food waste was found to be the main contributor to odor emission in mixed MSW, with H₂S generation potential of 48.4 μg kg^?1 and NH₃ generation potential of 4742 μg kg^?1. Fruit waste was another source for NH₃ generation, with 3933 μg kg^?1 NH₃ generation potential. Meanwhile, nitrogen (N) was released in a faster way than sulfur (S) in waste, since 31% and 46% of total NH₃ and H₂S were generated in the first 90 days after disposal, with 1811 and 72 μg kg^?1, and more emphasis should be placed in this initial period.

Implications:?Monitoring of odor generation from biowastes in MSW on a laboratory scale showed that food waste is the main source for NH₃ and H₂S generation, whereas waste fruit is another main contributor for NH₃ released. Generally, N was released in a faster way than S from mixed-waste landfilling.     

Measurement and Analysis of the Relationship between Ammonia,Acid Gases,and Fine Particles in Eastern North Carolina

Abstract

An annular denuder system, which consisted of a cyclone separator; two diffusion denuders coated with sodium carbonate and citric acid, respectively; and a filter pack consisting of Teflon and nylon filters in series, was used to measure acid gases, ammonia (NH₃), and fine particles in the atmosphere from April 1998 to March 1999 in eastern North Carolina (i.e., an NH₃?rich environment). The sodium carbonate denuders yielded average acid gas concentrations of 0.23 μg/m³ hydrochloric acid (standard deviation [SD] ± 0.2 μg/m³); 1.14 μg/m³ nitric acid (SD ± 0.81 μg/m³), and 1.61 μg/m³ sulfuric acid (SD ± 1.58 μg/m³). The citric acid denuders yielded an average concentration of 17.89 μg/m³ NH₃ (SD ± 15.03 μg/m³). The filters yielded average fine aerosol concentrations of 1.64 μg/m³ ammonium (NH₄ ⁺;SD ± 1.26 μg/m³); 0.26 μg/m³ chloride (SD ± 0.69 μg/m³), 1.92 μg/m³ nitrate (SD ± 1.09 μg/m³), and 3.18 μg/m³ sulfate (SO₄ ^2?; SD ± 3.12 μg/m³). From seasonal variation, the measured particulates (NH₄ ⁺,SO₄ ^2?, and nitrate) showed larger peak concentrations during summer, suggesting that the gas-to-particle conversion was efficient during summer. The aerosol fraction in this study area indicated the domination of ammonium sulfate particles because of the local abundance of NH₃, and the long-range transport of SO₄ ^2? based on back trajectory analysis. Relative humidity effects on gas-to-particle conversion processes were analyzed by particulate NH₄ ⁺ concentration originally formed from the neutralization processes with the secondary pollutants in the atmosphere.     

超声波光催化协同降解对甲基苯磺酸水溶液的机理研究

采用超声波与光催化联合法对模拟废水中难生物降解的对甲基苯磺酸(4-TSA)进行降解实验研究,借助紫外光谱、红外光谱、质谱、气相色谱、高效液相色谱、化学需氧量和总有机碳的检测结果对反应机理进行了初步探讨.实验结果表明:超声波和光催化之间存在着协同效应;当溶液初始质量浓度30 mg/L,光催化剂TiO2投加量为100 mg...     

Monitoring Deposition of Nitrogen-Containing Compounds in a High-Elevation Forest Canopy

Measurements of airborne (gaseous and aerosol), cloud water, and precipitation concentrations of nitrogen compounds were made at Mt. Mitchell State Park (Mt. Gibbs, ~2006 m MSL), North Carolina, during May through September of 1988 and 1989, An annular denuder system was used to ascertain gaseous (nitric acid, nitrous acid, and ammonia) and particulate (nitrate and ammonium) nitrogen species, and a chemiluminescence nitrogen oxides analyzer was used to measure nitric oxide and nitrogen dioxide. Measurements of NO₃ ^? and NH₄ ⁺ ions in cloud and rain water samples were made during the same time period. Mean concentrations of gaseous nitric acid, nitrous acid, and ammonia were 1.14 μg/m³, 0.3 μg/m³, and 0.62 μg/m³ for 1988, and 1.40 μg/m³,0.3 μg/m³, and 1.47 μg/m³ for 1989, respectively. Fine particulate nitrate and ammonium ranged from 0.02 to 0.21 μg/m³ and 0.01 to 4.72 μg/m³ for 1988, and 0.1 to 0.78 μg/m³ and 0.24 to 2.32 μg/m³ for 1989, respectively. The fine aerosol fraction was dominated by ammonium sulfate particles. Mean concentrations of nitrate and ammonium ions in cloud water samples were 238 and 214 μmol/l in 1988, and 135 and 147 μmol/l in 1989, respectively. Similarly, the concentrations of NO₃ and NH₄ ⁺ in precipitation were 26.4 and 14.0 μmol/l in 1988, and 16.6 and 15.2 μmol/l in 1989, respectively. The mean total nitrogen deposition due to wet, dry, and cloud deposition processes was estimated as ~30 and ~40 kg N/ha/year (i.e., ~10 and ~13 kg N/ha/growing season) for 1988 and 1989. Based on an analytical analysis, deposition to the forest canopy due to cloud interception, precipitation, and dry deposition processes was found to contribute ~60, ~20, and ~20 percent, respectively, of the total nitrogen deposition.     

亚铁离子生物氧化-还原法连续脱除硫化氢

为了降低工业废气中的硫化氢去除工艺成本和运行费用,对三价铁盐吸收与氧化亚铁硫杆菌对Fe²⁺的生物氧化联合作用脱除H₂S进行了研究。通过生物氧化塔中的固定化氧化亚铁硫杆菌细胞再生的Fe³⁺溶液,在H₂S还原吸收塔中脱除H₂S。通过单因素实验分别优化了生物氧化塔和H₂S吸收塔的运行参数,在生物氧化塔曝气量为150 L/h,停留时间为11 h,吸收液中Fe³⁺浓度为0.121~0.143 mol/L,吸收液流量为0.3 L/h,进气量为100 L/h条件下,进气中H₂S浓度分别为2.28和9.11 mg/L,系统连续运行至200 min时趋于相对稳定,当系统连续运行稳定时,H₂S的脱除率可分别达到95%和91%,脱除效果显著。     

The Recovery of Ammonia and Hydrogen Sulflde from Ground-Level Area Sources Using Dynamic Isolation Flux Chambers: Bench-Scale Studies

Abstract

Controlled bench-scale laboratory experiments were conducted to evaluate the recovery of ammonia (NH₃) and hydrogen sulflde (H₂S) from dynamic isolation flux chambers. H₂S (80–4000 ppb) and NH₃ (5000–40,000 ppb) samples were diffused through the flux chamber to simulate ground level area source emissions while measuring the inlet and outlet flux chamber concentrations simultaneously. Results showed that the recovery of H₂S during a 30-min sampling time was almost complete for concentrations >2000 ppb. At the lowest concentration of 80 ppb, 92.55% of the H₂S could be recovered during the given sampling period. NH₃ emissions exhibited similar behavior between concentrations of 5000–40,000 ppb. Within the 30-min sampling period, 92.62% of the 5000-ppb NH₃ sample could be recovered. Complete recovery was achieved for concentrations >40,000 ppb. Predictive equations were developed for gas adsorption. From these equations, the maximum difference between chamber inlet and outlet concentrations of NH₃ or H₂S was predicted to be 7.5% at the lowest concentration used for either gas. In the calculation of emission factors for NH₃ and H₂S, no adsorption correction factor is recommended for concentrations >37,500 ppb and 2100 ppb for NH₃ and H₂S, respectively. The reported differences in outlet and inlet concentration above these ranges are outside the full-scale sensitivity of the gas sensing equipment. The use of 46–90 m of Teflon tubing with the flux chambers has apparently no effect on gas adsorption, because recovery was completed almost instantaneously at the beginning of the tests.     

Simultaneous sampling of NH3, HNO3, HC1, SO2 and H2O2 in ambient air by a wet annular denuder system

A new sampling device is described for the simultaneous collection of NH₃, HNO₃, HCl, SO₂ and H₂O₂ in ambient air. The apparatus is based on air sampling by two parallel annular denuder tubes. The gases are collected by absorption in solutions present in the annulus of the denuder tubes. After a sampling time of 30 min at flow rate of 32 ℓ min⁻¹ the solutions are extracted from the denuders and analyzed off-line. The detection limits of NH₃, HNO₃, HCL and SO₂ are in the order of 0.1–0.5 μm⁻³. For H₂O₂ the detection limit is 0.01 μm⁻³. The reproducibility is 5–10% at the level of ambient air concentrations. Comparison of this novel technique with existing methods gives satisfactory results. The compact set-up offers the possibility of field experiments without the need of extensive equipment.     

Quality Assured Measurements of Animal Building Emissions: Gas Concentrations

Abstract

Comprehensive field studies were initiated in 2002 to measure emissions of ammonia (NH₃), hydrogen sulfide (H₂S), carbon dioxide (CO₂), methane (CH₄), nonmethane hydrocarbons (NMHC), particulate matter <10 µm in diameter, and total suspended particulate from swine and poultry production buildings in the United States.

This paper focuses on the quasicontinuous gas concentration measurement at multiple locations among paired barns in seven states. Documented principles, used in air pollution monitoring at industrial sources, were applied in developing quality assurance (QA) project plans for these studies. Air was sampled from multiple locations with each gas analyzed with one high quality commercial gas analyzer that was located in an environmentally controlled on-farm instrument shelter. A nominal 4 L/min gas sampling system was designed and constructed with Teflon wetted surfaces, bypass pumping, and sample line flow and pressure sensors. Three-way solenoids were used to automatically switch between multiple gas sampling lines with ≥10 min sampling intervals. Inside and outside gas sampling probes were between 10 and 115 m away from the analyzers. Analyzers used chemiluminescence, fluorescence, photoacoustic infrared, and photoionization detectors for NH₃, H₂S, CO₂, CH₄, and NMHC, respectively. Data were collected using personal computer-based data acquisition hardware and software. This paper discusses the methodology of gas concentration measurements and the unique challenges that livestock barns pose for achieving desired accuracy and precision, data representativeness, comparability and completeness, and instrument calibration and maintenance.     

Biological elimination of H2S and NH3 from wastegases by biofilter packed with immobilized heterotrophic bacteria

Biotreatment of various ratios of H₂S and NH₃ gas mixtures was studied using the biofilters, packed with co-immobilized cells (Arthrobacter oxydans CH8 for NH₃ and Pseudomonas putida CH11 for H₂S). Extensive tests to determine removal characteristics, removal efficiency, removal kinetics, and pressure drops of the biofilters were performed. To estimate the largest allowable inlet concentration, a prediction model was also employed. Greater than 95% and 90% removal efficiencies were observed for NH₃ and H₂S, respectively, irrespective of the ratios of H₂S and NH₃ gas mixtures. The results showed that H₂S removal of the biofilter was significantly affected by high inlet concentrations of H₂S and NH₃. As high H₂S concentration was an inhibitory substrate for the growth of heterotrophic sulfur-oxidizing bacteria, the activity of H₂S oxidation was thus inhibited. In the case of high NH₃ concentration, the poor H₂S removal efficiency might be attributed to the acidification of the biofilter. The phenomenon was caused by acidic metabolite accumulation of NH₃. Through kinetic analysis, the presence of NH₃ did not hinder the NH₃ removal, but a high H₂S concentration would result in low removal efficiency. Conversely, H₂S of adequate concentrations would favor the removal of incoming NH₃. The results also indicated that maximum inlet concentrations (model-estimated) agreed well with the experimental values for space velocities of 50–150 h⁻¹. Hence, the results would be used as the guideline for the design and operation of biofilters.     

Fenton氧化-序批式膜生物反应器耦合处理干法腈纶废水

采用Fenton氧化-序批式膜生物反应器(SBMBR)组合工艺处理干法腈纶废水。结果表明,在废水初始pH值为3.0,H2O2投加量为90.0 mmol/L,Fe2+投加量为20.0 mmol/L,反应时间为2.0 h的条件下,Fenton氧化预处理对腈纶生产废水的COD去除率达到47.0%以上,COD由1 091 mg/L降至560 mg/L,废水的BOD5/COD由0.32升至0.69,废水的可生化性得到显著提高。Fenton处理出水与丙烯腈废水等比例混合后,采用SBMBR进行生化处理,在水力停留时间为24 h,90 min缺氧/150 min好氧交替运行的条件下,COD、NH4+-N和TN的平均去除率分别为71.7%、97.2%和47.4%,碳源不足是限制TN去除效果的主要影响因素。在无外加碳源的条件下,组合工艺处理后出水COD和NH4+-N浓度分别为117 mg/L和1.7 mg/L,出水水质可以稳定达到国家一级排放标准(GB8978-1996)。     

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.     

Abatement of Ammonia and Hydrogen Sulfide Emissions from a Swine Lagoon Using a Polymer Biocover

ABSTRACT

The purpose of this research was to determine the efficiency of a polymer biocover for the abatement of H₂S and NH₃ emissions from an east-central Missouri swine lagoon with a total surface area of 7800 m². The flux rate of NH₃, H₂S, and CH₄ was monitored continuously from two adjacent, circular (d = 66 m) control and treatment plots using a nonintrusive, micrometeorological method during three independent sampling periods that ranged between 52 and 149 hr. Abatement rates were observed to undergo a temporal acclimation event in which NH₃ abatement efficiency improved from 17 to 54% (p = <0.0001 to 0.0005) and H₂S abatement efficiency improved from 23 to 58% (p < 0.0001) over a 3-month period. The increase in abatement efficiency for NH₃ and H₂S over the sampling period was correlated with the development of a stable anaerobic floc layer on the bottom surface of the biocover that reduced mass transfer of NH₃ and H₂S across the surface. Analysis of methanogenesis activity showed that the biocover enhanced the rate of anaerobic digestion by 25% when compared with the control. The biocover-enhanced anaerobic digestion process was shown to represent an effective mechanism to counteract the accumulation of methanogenic substrates in the biocovered lagoon.     

Photochemical degradation of ciprofloxacin in UV and UV/H2O2 process: kinetics, parameters, and products

Photochemical degradation of fluoroquinolone ciprofloxacin (CIP) in water by UV and UV/H₂O₂ were investigated. The degradation rate of CIP was affected by pH, H₂O₂ dosage, as well as the presence of other inorganic components. The optimized pH value and H₂O₂ concentration were 7.0 and 5 mM. Carbonate and nitrate both impeded CIP degradation. According to liquid chromatography–tandem mass spectrometry analysis, four and 16 products were identified in UV and UV/H₂O₂ system, respectively. Proposed degradation pathways suggest that reactions including the piperazinyl substituent, quinolone moiety, and cyclopropyl group lead to the photochemical degradation of CIP. Toxicity of products assessed by Vibrio qinghaiensis demonstrated that UV/H₂O₂ process was more capable on controlling the toxicity of intermediates in CIP degradation than UV process.     

粉煤灰协同微波-Fenton氧化法处理活性艳蓝KN-R染料废水

以粉煤灰联合微波-Fenton氧化工艺处理活性艳蓝KN-R生产废水,考察了粉煤灰投加量及吸附时间对处理效果的影响,并通过正交实验对微波-Fenton工艺参数进行了优化。实验结果表明,粉煤灰絮凝吸附与微波-Fenton氧化具有协同效应;在粉煤灰投加量为40 g/L,搅拌吸附时间为20 min,滤液pH值为4,Fe2＋和H2O2投加量分别为3.6 mmol/L和0.15 mol/L,微波功率为200 W,辐射反应时间为4 min的优化条件下,染料废水的处理效果最好,COD和色度的去除率分别达到90.90%和99.98%。     

Effects of ammonia on methane oxidation in landfill cover materials

The effects of ammonia (NH₃) on CH₄ attenuation in landfill cover materials consisting of landfill cover soil (LCS) and aged municipal solid waste (AMSW), at different CH₄ concentrations, were investigated. The CH₄ oxidation capacities of LCS and AMSW were found to be significantly affected by the CH₄ concentration. The maximum oxidation rates for LCS and AMSW were obtained at CH₄ concentrations of 5 % and 20 %(v/v), respectively, within 20 days. CH₄ biological oxidation in AMSW was significantly inhibited by NH₃ at low CH₄ concentrations (5 %, v/v) but highly stimulated at high levels (20 % and 50 %, v/v). Oxidation in LCS was stimulated by NH₃ at all CH₄ concentrations due to the higher conversion of the nitrogen in NH₃ in AMSW than in LCS. NH₃ increases CH₄ oxidation in landfill cover materials.