Carbon Disulfide and Hydrogen Sulfide Removal with a Peat Biofilter

ABSTRACT

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.     

Oxidation of gas mixtures containing dimethyl sulfide, hydrogen sulfide, and methanethiol using a two-stage biotrickling filter

A biofiltration technique was developed for removing a mixture of hydrogen sulfide (H2S), methanethiol (MeSH), and dimethyl sulfide (Me2S) from waste gases. Since H2S, especially at high concentrations, disturbs the removal of Me2S, two biotrickling filters with different microbes and operating pH levels were connected in series to create a two-stage system. Different loads of these gases were studied in order to determine their impact on the removal capacity of the system. The microbial consortia for these filters were enriched from the sludge of a Finnish refinery with bubbling H2S or Me2S. Acclimation for Me2S took 2 weeks, though no acclimation time was needed for the other gases. The first filter, at a pH of 2, removed most of the H2S and some of the MeSH and Me2S. The second filter, at a pH of approximately 6.5, removed the rest of the MeSH and most of the Me2S. The total maximum loads of the whole two-stage biotrickling filter were 1150 g/m3/day for H2S-S (suffix S indicates the results are counted as sulfur amounts), 879 g/m3/day for Me2S-S, and 66 g/m3/day for MeSH-S treated in a gas mixture. The average removal efficiencies for all gases tested were 99% or higher.     

Removal of formaldehyde, methanol, dimethylether and carbon monoxide from waste gases of synthetic resin-producing industries

The removal of mixtures of gas-phase pollutants released from formaldehyde- and formaldehyde resin-producing industries was studied in different bioreactor systems. The waste gases contained formaldehyde, methanol, dimethylether and carbon monoxide. The use of a hybrid two-stage bioreactor, composed of a biotrickling filter and a conventional biofilter connected in series, led to very high elimination capacities and removal efficiencies close to 100% for overall pollutant loads exceeding 600g m(-3)h(-1). The presence of low concentrations of dimethylether in the gaseous mixture did not have a significant effect on the removal of formaldehyde or methanol under our operating conditions, although moderate concentrations of these compounds did negatively affect the biodegradation of dimethylether. When a mixture of all four compounds, at concentrations around 100, 100, 50 and 50mg m(-3) for formaldehyde, methanol, carbon monoxide and dimethylether, respectively, was fed to a conventional biofilter, removal efficiencies higher than 80% were obtained for the first three pollutants at empty bed retention time values above 30s. On the other hand, dimethylether was removed to a lower extent, although its reduced environmental impact allows to conclude that these results were satisfactory.     

Biotreatment of H2S- and NH3-containing waste gases by co-immobilized cells biofilter

Gas mixture of H2S and NH3 in this study has been the focus in the research area concerning gases generated from the animal husbandry and the anaerobic wastewater lagoons used for their treatment. A specific microflora (mixture of Thiobacillus thioparus CH11 for H2S and Nitrosomonas europaea for NH3) was immobilized with Ca-alginate and packed inside a glass column to decompose H2S and NH3. The biofilter packed with co-immobilized cells was continuously supplied with H2S and NH3 gas mixtures of various ratios, and the removal efficiency, removal kinetics, and pressure drop in the biofilter was monitored. The results showed that the efficiency remained above 95% regardless of the ratios of H2S and NH3 used. The NH3 concentration has little effect on H2S removal efficiency, however, both high NH3 and H2S concentrations significantly suppress the NH3 removal. Through product analysis, we found that controlling the inlet ratio of the H2S/NH3 could prevent the biofilter from acidification, and, therefore, enhance the operational stability. Conclusions from bioaerosol analysis and pressure drop in the biofilter suggest that the immobilized cell technique creates less environmental impact and improves pure culture operational stability. The criteria for the biofilter operation to meet the current H2S and NH3 emission standards were also established. To reach Taiwan's current ambient air standards of H2S and NH3 (0.1 and 1 ppm, respectively), the maximum inlet concentrations should not exceed 58 ppm for H2S and 164 ppm for NH3, and the residence time be kept at 72 s.     

Operational characteristics of effective removal of H2S and NH3 waste gases by activated carbon biofilter

Simultaneous removal of hydrogen sulfide (H2S) and ammonia (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.     

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.     

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.     

有机复合填料生物滤床对甲苯气体的净化

利用一种新型有机复合填料作为生物滤床中微生物的附着载体,接种经过驯化筛选的专性甲苯降解菌,填装于生物过滤塔中净化低浓度甲苯气体。研究了新型有机复合填料在长期运行时的情况,考察了进气流量、入口浓度、床层温度和填料湿度对生物滤床的影响,最终经过优化得出,此种填料的生物滤床能够为微生物提供良好的附着生长环境,并能保持滤床的高效稳定运行,当进气流量为0.4 m3/h,入口浓度为400 mg/m3,床层温度为30℃,填料湿度为50%时,生化去除量达到30.6 g/(m3·h),并且在此条件下滤床具有良好的耐冲击性能。     

Treatment of 1,3-Butadiene in an Air Stream by a Biotrickling Filter and a Biofilter

ABSTRACT

This paper presents results obtained from a performance study on the biotreatment of 1,3-butadiene in an air stream using a reactor that consisted of a two-stage, in-series biotrickling filter connected with a three-stage, in-series biofilter. Slags and pig manure-based media were used as packing materials for the biotrickling filter and the biofilter, respectively. Experimental results indicated that, for the biotrickling filter portion, the butadiene elimination capacities were below 5 g/m³/hr for loadings of less than 25 g/m³/hr, and the butadiene removal efficiency was only around 17%. For the biofilter portion, the elimination capacities ranged from 10 to 107 g/m³/hr for loadings of less than 148 g/m³/hr. The average butadiene removal efficiency was 75–84% for superficial gas velocities of 53–142 m/hr and a loading range of 10–120 g/m³/hr. The elimination capacity approached a maximum of 108 g/m³/hr for a loading of 150 g/m³/hr. The elimination rates of butadiene in both the biotrickling filter and biofilter were mass-transfer controlled for influent butadiene concentrations below about 600 ppm for superficial gas velocities of 29–142 m/hr. The elimination capacity was significantly higher in the biofilter than in the biotrickling filter. This discrepancy may be attributed to the higher mass-transfer coefficient and gas-solid interfacial area offered for transferring the gaseous butadiene in the biofilter.     

Sulfur toxicity and media capacity for H2S removal in biofilters packed with a natural or a commercial granular medium

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.     

pH对生物滤池处理含H_2S和NH_3混合恶臭气体的影响

研究了pH对生物滤池处理含H2S和NH3混合恶臭气体的影响,以及不同pH下的物质转化情况和去除机制。结果表明,不同pH下,生物滤池对H2S和NH3的去除率是不同的。在强酸性(pH为2左右)和中性(pH为7左右)条件下,H2S均有较好的去除效果,这分别归于嗜酸性硫细菌和非嗜酸性硫细菌的生物降解作用。低pH下,NH3的去除归于化学中和作用;中性(pH为7左右)条件下,NH3有较高的去除率,主要依靠生物硝化作用。通过考察pH对生物滤池处理效果的影响,确定了生物滤池处理含H2S和NH3混合恶臭气体的pH控制条件和去除机制,为恶臭气体生物处理工艺的选择提供依据。     

Biotreatment of hydrogen sulfide- and ammonia-containing waste gases by fluidized bed bioreactor

Gas mixtures of H2S and NH3 are the focus of this study of research concerning gases generated from animal husbandry and treatments of anaerobic wastewater lagoons. A heterotrophic microflora (a mixture of Pseudomonas putida for H2S and Arthrobacter oxydans for NH3) was immobilized with Ca-alginate and packed into a fluidized bed reactor to simultaneously decompose H2S and NH3. This bioreactor was continuously supplied with H2S and NH3 separately or together at various ratios. The removal efficiency, removal rate, and metabolic product of the bioreactor were studied. The results showed that the efficiency remained above 95% when the inlet H2S concentration was below 30 ppm at 36 L/hr. Furthermore, the apparent maximum removal and the apparent half-saturation constant were 7.0 x 10(-8) g-S/cell/day and 76.2 ppm, respectively, in this study. The element sulfur as a main product prevented acidification of the biofilter, which maintained the stability of the operation. As for NH3, the greater than 90% removal rate was achieved as long as the inlet concentration was controlled below 100 ppm at a flow rate of 27 L/hr. In the NH3 inlet, the apparent maximum removal and the apparent half-saturation constant were 1.88 x 10(-6) g-N/cell/day and 30.5 ppm, respectively. Kinetic analysis showed that 60 ppm of NH3 significantly suppressed the H2S removal by Pseudomonas putida, but H2S in the range of 5-60 ppm did not affect NH3 removal by Arthrobacter oxydans. Results from bioaerosol analysis in the bioreactor suggest that the co-immobilized cell technique applied for gas removal creates less environmental impact.     

Deodorization of dimethyl sulfide using a discharge approach at room temperature

The traditional technologies for odor removal of thiol usually create either secondary pollution for scrubbing, adsorption, and absorption processes, or sulfur (S) poisoning for catalytic incineration. This study applied a laboratory-scale radio-frequency plasma reactor to destructive percentage-grade concentrations of odorous dimethyl sulfide (CH3SCH3, or DMS). Odor was diminished effectively via reforming DMS into mainly carbon disulfide (CS2) or sulfur dioxide (SO2). The removal efficiencies of DMS elevated significantly with a lower feeding concentration of DMS or a higher applied rf power. A greater inlet oxygen (O2)/DMS molar ratio slightly improved the removal efficiency. In an O2-free environment, DMS was converted primarily to CS2, methane (CH4), acetylene (C2H2), ethylene (C2H4), and hydrogen (H2), with traces of hydrogen sulfide (H2S), methyl mercaptan (CH3SH), and dimethyl disulfide. In an O2-containing environment, the species detected were SO2, CS2, carbonyl sulfide, carbon dioxide (CO2), CH4, C2H4, C2H2, H2, formaldehyde, and methanol. Differences in yield of products were functions of the amounts of added O2 and the applied power. This study provided useful information for gaining insight into the reaction pathways for the DMS dissociation and the formation of products in the plasmolysis and conversion processes.     

闽南地区低温下复合填料强化生物滤柱除臭及微生物分析

通过搭建复合填料-生物滤柱反应装置,在厦门冬季低温环境下开展复合填料（蜂窝煤渣、活性炭、蜂窝沸石和陶粒）强化生物滤柱除臭研究,分析了除臭微生物群落组成特性。复合填料-生物滤柱装置在启动运行15 d时其COD去除率达到85%以上且保持稳定,对H₂S和NH₃的最大去除率可分别达到91.77%和82.53%,表明挂膜成功。菌群分析结果表明：以H₂S、NH₃等臭气喷淋液为基质的生物滤柱驯化挂膜过程会降低微生物的丰度和多样性;菌属Thiothrix、Ferruginibacter、Burkholderiaceae、Tahibacter、Dinghuibacter、Cloacibacterium和Kosakonia是除臭过程的优势功能微生物和臭气成分降解的贡献者。本研究阐明了复合填料生物膜内功能菌属对H₂S、NH₃等臭气喷淋液有机质的生物降解/转化机制,并进行了物料平衡分析;复合填料-生物滤柱装置对H₂S与NH₃的平均去除率分别达到90.77%和72.53%,具有良好的生物除臭效果与运行稳定性。本研究可为南方低温季节的污水臭气治理提供技术参考和理论支撑。     

Degradation Kinetics of Biofilter Media Treating Reduced Sulfur Odors and VOCs

ABSTRACT

A lab-scale study was conducted to determine the rate and extent of decomposition of three biofilter media materials—compost, hog fuel, and a mixture of the two in 1:1 ratio—used in biofiltration applied to removal of reduced sulfur odorous compounds from pulp mill air emissions. The rate of carbon mineralization, as a measure of biofilter media degradation, was determined by monitoring respiratory CO₂ evolution and measuring the changes in carbon and nitrogen fractions of the biofilter materials over a period of 127 days. Both ambient air and air containing reduced sulfur (RS) compounds were used, and the results were compared. After 127 days of incubation with ambient air, about 17% of the media carbon was evolved as CO₂ from compost as compared to 6 and 12% from hog fuel and the mixture, respectively. The decomposition showed sequential breakdown of carbon moieties, and three distinct stages were observed for each of the biofilter media. First-order rate kinetics were used to describe the decomposition stages. Decomposition rates in the initial stages were at least twice those of the following stages. Carbon mineralization showed close dependence on the C/N ratio of the biofilter material. Media decomposition was enhanced in the presence of RS gases as a result of increased bioactivity by sulfur-oxidizing bacteria and other microorganisms, thus reducing the media half-life by more than 50%. At higher concentrations of RS gases, the CO₂ evolution rates were proportionally lower than those at the low concentrations because of the limited acid buffering capacity of the biofilter materials.     

Co-treatment of hydrogen sulfide and methanol in a single-stage biotrickling filter under acidic conditions

Biofiltration of waste gases is cost-effective and environment-friendly compared to the conventional techniques for treating large flow rates of gas streams with low concentrations of pollutants. Pulp and paper industry off-gases usually contain reduced sulfur compounds, such as hydrogen sulfide and a wide range of volatile organic compounds (VOCs), e.g., methanol. It is desirable to eliminate both of these groups of compounds. Since the co-treatment of inorganic sulfur compounds and VOCs in biotrickling filters is a relatively unexplored area, the simultaneous biotreatment of H2S and methanol as the model VOC was investigated. The results showed that, after adaptation, the elimination capacity of methanol could reach around 236 g m(-3) h(-1) with the simultaneous complete removal (100%) of 12 ppm H2S when the empty bed residence time is 24 s. The pH of the system was around 2. Methanol removal was hardly affected by the presence of hydrogen sulfide, despite the low pH. Conversely, the presence of the VOC in the waste gas reduced the efficiency of H2S biodegradation. The maximal methanol removal decreased somewhat when increasing the gas flow rate. This is the first report on the degradation of methanol at such low pH in a biotrickling filter and on the co-treatment of H2S and VOCs under such conditions.     

不同挂膜方式生物滴滤塔处理含H2S恶臭气体

采用菌剂挂膜,活性污泥挂膜和自然挂膜3种不同方式形成生物滴滤塔,考察挂膜方式对生物滴滤塔去除H2s恶臭气体的影响。结果表明,当进气H2S浓度为5mg／m3时,菌剂挂膜、活性污泥挂膜、自然挂膜形成的生物滴滤塔出气H2s浓度分别为15．7～17．4、11．6～14．8和15．0～15．9μg／m3;塔内压降分别为3—4mm水柱、6mm水柱和4—5mm水柱;喷淋后滤出液中硫酸根的浓度分别为14、22和17mg／L,硫的转化率分别为45％、60％和50％。当进气H2S浓度增大至7mg／m3时,3个塔经过7d的调整后,均能达到稳定状态,稳定后3个塔中出气H2s浓度和压降基本没变,喷淋后滤出液中硫酸根浓度依次增大至25、31和30mg／L左右。采用活性污泥挂膜形成的生物滴滤塔处理H2s的能力比菌剂挂膜和自然挂膜的高。     

复合生物滤池处理H2S和NH3的挂膜与工艺条件

采用复合生物滤池(生物滴滤池 生物过滤池)处理H2S和NH3组成的混合恶臭气体,填料分别为经表面改性的天然斜发沸石和木屑.实验研究了该工艺的驯化挂膜情况和主要工艺条件,结果表明,天然斜发沸石和木屑改性后,驯化挂膜周期为10～14 d,比文献中颗粒活性炭挂膜缩短14～18 d.复合生物滤池的最佳工艺条件为:高度120 cm,循环液流量4.56 L/h.同时,生物滴滤池处理水溶性好的NH3气体效果较生物过滤池好,而生物过滤池处理水溶性差的H2S气体较生物滴滤池好.因此,复合生物滤池可用于处理不同水溶性的混合恶臭气体.     

Removal of ammonia by biofilters: a study with flow-modified system and kinetics

The characteristics of ammonia removal by two types of biofilter (a standard biofilter with vertical gas flow and a modified biofilter with horizontal gas flow) were investigated. A mixture of organic materials such as compost, bark, and peat was used as the biofilter media based on the small-scale column test for media selection. Complete removal capacity, defined as the maximum inlet load of ammonia that was completely removed, was obtained. The modified biofilter showed complete removal up to 1.0 g N/kg dry material/day. However, the removal capacity of the standard biofilter started to deviate from complete removal around 0.4 g N/kg dry material/day, indicating that the modified biofilter system has higher removal efficiency than the standard upflow one. In kinetic analysis of the biological removal of ammonia in each biofilter system, the maximum removal rate, Vm, was 0.93 g N/kg dry material/day and the saturation constant, Ks, was 32.55 ppm in the standard biofilter. On the other hand, the values of Vm and Ks were 1.66 g N/kg dry material/day and 74.25 ppm, respectively, in the modified biofilter system.     

生物催化氧化法脱除H2S的试验研究

针对H2S污染的严峻形势,构建了包括催化再生装置和生物滴滤器的生物催化氧化装置。该装置以沸石为填料,以氧化亚铁硫杆菌为脱硫菌种,通过微生物和Fe3+的双重氧化作用高效脱除H2S。试验确定了装置的适宜喷淋量和沸石的最佳粒径。在温度为30℃,进气量为0.25 m3/h,进气H2S浓度为2500mg/m3,喷淋量为1000mL/h,喷淋液的pH值为1.97、Fe3+浓度为0.05 mol/L的条件下,出气H2S浓度足以达到GB14554-93规定的一级厂界标准值。试验证明,生物催化氧化法是一种新型高效的脱硫技术,应进一步开展中试研究。