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.     

Biological sweetening of energy gases mimics in biotrickling filters

Removal of hydrogen sulfide from waste and energy-rich gases is required, not only because of environmental health and safety reasons, but also because of operational reasons if such gases have to be used for energy generation. A biotrickling filter for the removal of ultra-high concentrations of H2S from oxygen-poor gases is proposed and studied in this work. Two laboratory-scale biotrickling filters were used to study the startup period and to determine the long-term performance of the gas sweetening process. The inlet H2S concentration ranged from 900 to 12000ppmv and two different packing materials were investigated. There was no toxicity effect observed even at a the highest H2S concentration, and maximum elimination capacities of 280 and 250g H2Sm(-3)h(-1) were obtained at gas contact times of 167 and 180s, respectively. Elemental sulfur and sulfate were found to be the most abundant end-products of the biological oxidation of sulfide when operated under microaerophilic conditions. The biotrickling filter was able to quickly recover its nominal performance after different load increases and system shutdowns simulating field operation. The results reported here show that biotreatment can be an interesting alternative to conventional gas sweetening systems normally used for such applications.     

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.     

The control of mercury vapor using biotrickling filters

The feasibility of using biotrickling filters for the removal of mercury vapor from simulated flue gases was evaluated. The experiments were carried out in laboratory-scale biotrickling filters with various mixed cultures naturally attached on a polyurethane foam packing. Sulfur oxidizing bacteria, toluene degraders and denitrifiers were used and compared for their ability to remove Hg 0 vapor. In particular, the biotrickling filters with sulfur oxidizing bacteria were able to remove 100% of mercury vapor, with an inlet concentration of 300-650 microg m(-3), at a gas contact time as low as six seconds. 87-92% of the removed mercury was fixed in or onto the microbial cells while the remaining left the system with the trickling liquid. The removal of mercury vapors in a biotrickling filter with dead cells was almost equivalent to this in biotrickling filters with live cells, indicating that significant abiotic removal mechanisms existed. Sulfur oxidizing bacteria biotrickling filters were the most effective in controlling mercury vapors, suggesting that sulfur played a key role. Identification of the location of metal deposition and of the form of metal was conducted using TEM, energy dispersive X-ray analysis (EDAX) and mercury elution analyses. The results suggested that mercury removal was through a series of complex mechanisms, probably both biotic and abiotic, including sorption in and onto cellular material and possible biotransformations. Overall, the study demonstrates that biotrickling filters appear to be a promising alternative for mercury vapor removal from flue gases.     

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.     

生物滴滤塔处理有机废气的填料选择研究

以含低浓度乙酸、正己烷和苯乙烯的混合有机气体模拟实际有机废气,采用实验室规模的生物滴滤塔处理有机废气,并比较了海绵、珊瑚石、陶粒和空心塑料小球4种填料的性能。结果表明:(1)生物滴滤塔启动时间最短的为海绵生物滴滤塔(约20d),其次为陶粒生物滴滤塔(约25d),启动时间较长的为珊瑚石生物滴滤塔(约35d)和空心塑料小球生物滴滤塔(约40d)。(2)在稳定运行期,不同填料生物滴滤塔对水溶性和极性较强的乙酸的去除率差异尤为明显,对正己烷和苯乙烯的去除率差异相对较小。(3)4种填料生物滴滤塔中的异养细菌数量依次为海绵>陶粒>珊瑚石>空心塑料小球。运行80d时,海绵、陶粒、珊瑚石和空心塑料小球生物滴滤塔中的异养细菌数量分别达5.9×108、4.8×108、3.6×108、3.0×108 cfu/g(以单位质量干填料计)。(4)在相同的进气流速下,4种填料生物滴滤塔的填料层压力降依次为珊瑚石>陶粒>空心塑料小球>海绵。(5)海绵和陶粒较适宜作为生物滴滤塔的填料。     

Biological treatment process of air loaded with an ammonia and hydrogen sulfide mixture

The physico-chemical characteristics of granulated sludge lead us to develop its use as a packing material in air biofiltration. Then, the aim of this study is to investigate the potential of unit systems packed with this support in terms of ammonia and hydrogen sulfide emissions treatment. Two laboratory scale pilot biofilters were used. A volumetric load of 680 g H2S m(-3) empty bed day(-1) and 85 g NH3 m(-3) empty bed day(-1) was applied for eight weeks to a unit called BGSn (column packed with granulated sludge and mainly supplied with hydrogen sulfide); a volumetric load of 170 g H2S m(-3) empty bed day(-1) and 340 g NH3 m(-3) empty bed day(-1) was applied for eight weeks to the other called BGNs (column packed with granulated sludge and mainly supplied with ammonia). Ammonia and hydrogen sulfide elimination occur in the biofilters simultaneously. The hydrogen sulphide and ammonia removal efficiencies reached are very high: 100% and 80% for BGSn; 100% and 80% for BGNs respectively. Hydrogen sulfide is oxidized into sulphate and sulfur. The ammonia oxidation products are nitrite and nitrate. The nitrogen error mass balance is high for BGSn (60%) and BGNs (36%). This result could be explained by the denitrification process which would have occurred in anaerobic zones. High percentages of ammonia or hydrogen sulfide are oxidized on the first half of the column. The oxidation of high amounts of hydrogen sulfide would involve some environmental stress on nitrifying bacterial growth and activity.     

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.     

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.     

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。     

Effectiveness and mechanisms of hydrogen sulfide adsorption by camphor-derived biochar

The characteristics and mechanisms of hydrogen sulfide (H2S) adsorption on a biochar through pyrolysis at various temperatures (100 to 500 degrees C) were investigated. The biochar used in the current study was derived from the camphor tree (Cinnamomum camphora). The samples were ground and sieved to produceparticle sizes of 0.4 mm to 1.25 mm, 0.3 mm to 0.4 mm, and <0.3 mm. The H2S breakthrough capacity was measured using a laboratory-designed test. The surface properties of the biochar were characterized using pH and Fourier-transform infrared spectroscopy (FTIR) analysis. The results obtained demonstrate that all camphor-derived biochars were effective in H2S sorption. Certain threshold ranges ofthepyrolysis temperature and surfacepH were observed, which, when exceeded, have dramatic effects on the H2S adsorption capacity. The sorption capacity ranged from 1.2 mg/g to 121.4 mg/g. The biochar with 0.3 mm to 0.4 mm particle size possesses a maximum sorption capacity at 400 degrees C. The pH and FTIR analysis results showed that carboxylic and hydroxide radical groups were responsible for H2S sorption. These observations will be helpful in designing biochar as engineered sorbents for the removal of H2S.     

PTR-MS measurement of partition coefficients of reduced volatile sulfur compounds in liquids from biotrickling filters

Biological air filtration for reduction of emissions of volatile sulfur compounds (e.g., hydrogen sulfide, methanethiol and dimethyl sulfide) from livestock production facilities is challenged by poor partitioning of these compounds into the aqueous biofilm or filter trickling water. In this study, Henry’s law constants of reduced volatile sulfur compounds were measured for deionized water, biotrickling filter liquids (from the first and second stages of a two-stage biotrickling filter), and NaCl solutions by a dynamic method using Proton-Transfer-Reaction Mass Spectrometry (PTR-MS) at a temperature range of 3–45 °C. NaCl solutions were used to estimate salting-out constants up to an ionic strength of 0.7 M in order to evaluate the effect of ionic strength on partitioning between air and biofilter liquids. Thermodynamic parameters (enthalpy and entropy of phase exchange) were obtained from the measured partition coefficients as a function of temperature. The results show that the partition coefficients of organic sulfur compounds in the biotrickling filter liquids were generally very close to the corresponding partition coefficients in deionized water. Based on the estimated ionic strength of biofilter liquids, it is assessed that salting-out effects are of no importance for these compounds. For H₂S, a higher enthalpy of air–liquid partitioning was observed for 2nd stage filter liquid, but not for 1st stage filter liquid. In general, the results show that co-solute effects for sulfur compounds can be neglected in numerical biofilter models and that the uptake of volatile sulfur compounds in biotrickling filter liquids cannot be increased by decreasing ionic strength.     

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.     

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。     

Removal of hydrogen sulfide and sulfur dioxide by carbons impregnated with triethylenediamine

Activated carbon (AC) adsorption has long been considered to be a readily available technology for providing protection against exposure to acutely toxic gases. However, ACs without chemical impregnation have proven to be much less efficient than impregnated ACs in terms of gas removal. The impregnated ACs in current use are usually modified with metalloid impregnation agents (ASC-carbons; copper, chromium, or silver) to simultaneously enhance the chemical and physical properties of the ACs in removing specific poisonous gases. These metalloid agents, however, can cause acute poisoning to both humans and the environment, thereby necessitating the search for organic impregnation agents that present a much lower risk. The aim of the study reported here was to assess AC or ASC-carbon impregnated with triethylenediamine (TEDA) in terms of its adsorption capability for simulated hydrogen sulfide (H2S) and sulfur dioxide (SO2) gases. The investigation was undergone in a properly designed laboratory-scale and industrial fume hood evaluation. Using the system reported here, we obtained a significant adsorption: the removal capability for H2S and SO2 was 375 and 229 mg/g-C, respectively. BET measurements, element analysis, scanning electron microscopy, and energy dispersive spectrometry identified the removal mechanism for TEDA-impregnated AC to be both chemical and physical adsorption. Chemical adsorption and oxidation were the primary means by which TEDA-impregnated ASC-carbons removed the simulated gases.     

Abiotic and biological mechanisms of nitric oxide removal from waste air in biotrickling filters

Nitric oxide (NO) may participate in the ozone layer depletion and forming of nitric acid. Abiotic and biological mechanisms of NO removal from waste gases were studied in a biotrickling filter. The abiotic NO removal rate in the biotrickling filter was estimated by a review of the literature. The abiotic and biological removals were also verified in the biotrickling filter. The result has shown that chemical oxidation and bionitrification were both involved in the NO removal. It was found that the NO removal in high concentration (approximately 1000 ppm or higher) was in large measure the result of abiotic removal in both gas-phase and liquid-phase reactions. When NO concentration is low (less than approximately 100 ppm), bionitrification was the main process in the NO removal process in the biotrickling filter.     

硫化镍异相结晶法处理含镍废水

针对含络合剂的重金属废水,以含镍废水为例,探索了以气体硫化氢为结晶药剂的硫化镍异相结晶技术。废水以薄层液膜方式铺展于结晶载体表面,硫化氢气体穿过气液界面进入液相,硫离子与金属离子在载体表面异相结晶析出,重金属得以去除。以含酒石酸的模拟化学镀镍废水为对象,静态实验与动态实验均表明该技术具有可行性,硫化镍沉淀在结晶载体表面异相结晶析出,且附着稳定;络合剂对反应影响小;进水流速为4 mL/min,硫化钠流速为0.65 g/min,氮气流速为0.16 L/min时,出水镍浓度为49～53 mg/L,单位面积滤布表面结晶平均去除镍量为0.98 g/(m2.h)。     

Middle-thermophilic sulfur-oxidizing bacteria Thiomonas sp. RAN5 strain for hydrogen sulfide removal

Hydrogen sulfide (H2S) is one of the most toxic and offensively odorous gases and is generated in anaerobic bioreactors. A middle-thermophilic sulfur-oxidizing bacterium (SOB), Thiomonas sp. strain RAN5, was isolated and applied for H2S removal from both artificial and anaerobically digested gas. When a bioreactor containing medium inoculated with RAN5 was aerated continuously with artificial gas (containing 100 ppm H2S) at 45 degrees C for 156 hr, the H2S concentration in the vented gas was reduced by 99%. This was not affected by the presence of other microbes in the bioreactor The H2S removal efficiency of the RAN5 bioreactor for anaerobically digested gas was greater than 99% at influent H2S concentrations ranging from 2 to 1800 ppm; the efficiency decreased to 90% at influent H2S concentrations greater than 2000 ppm. Thiomonas sp. strain RAN5 cannot survive at room temperature, and thus its leakage from a wastewater treatment plant would not damage sewage systems. These data suggest that Thiomonas sp. strain RAN5 may be a useful microorganism for H2S removal.     

Removal of nitric oxide in a biotrickling filter under thermophilic condition using Chelatococcus daeguensis

The development of a thermophilic biotrickling filter (BTF) system to inoculate a newly isolated strain of Chelatococcus daeguensis TAD1 for the effective treatment of nitric oxide (NO) is described. A bench-scale BTF was run under high concentrations of NO and 8% O2 in thermophilic aerobic environment. A novel aerobic denitrifier Chelatococcus daeguensis TAD1 was isolated from the biofilm of an on-site biotrickling filter and it showed a denitrifying capability of 96.1% nitrate removal rate in a 24 h period in aerobic environment at 50 degrees C, with no nitrite accumulation. The inlet NO concentration fluctuated between approximately 133.9 and 669.6 mg m-3 and kept on a steady NOx removal rate above 80% in an oxygen stream of 8%. The BTF system was able to consistently remove 80-93.7% NO when the inlet NO was 535.7 mg m-3 in an oxygen stream of 2-20%. The biological removal efficiency of NO at 50 degrees C is higher than that at 25 degrees C, suggesting that the aerobic denitrifier TAD1 display well denitrification performance under thermophilic condition. Starvation for 2, 4 and 8 days resulted in the re-acclimation times of Chelatococcus daeguensis TAD1 ranging between 4 and 16 hours. A longer recovery time than that for weekend shutdown will be required when a longer starvation occurs. The results presented here demonstrate the feasibility of biotrickling filter for the thermophilic removal of NOx from gas streams. Implications: A novel denitrifier Chelatococcus daeguensis TAD1 was isolated from an on-site biotrickling filter in aerobic environment at 50 degrees C. To date, C. daeguensis has not been previously reported to be an aerobic denitrifier. In this study, a thermophilic biotrickling filter system inoculated with Chelatococcus daeguensis TADI for treatment of nitric oxide is developed. In coal-fired power plants, influent flue gas stream for nitrogen oxides (NOx) removal typically exhibit temperatures between 50 and 60 degrees C. Traditionally, cooling gases to below 40 degrees C prior to biological treatment is inevitable, which is costly. Therefore, the application ofthermophilic microorganisms for the removal of nitric oxide (NO) at this temperature range would offer great savings and would greatly extend the applicability ofbiofilters and biotrickling filters. Until now there has not been any study published about thermophilic biological treatment of NO under aerobic condition.     

Biodegradation of hydrogen sulphide by inoculated Rhodococcus sp.zw11 in a pilot-scale biotrickling filter

A strain of autotrophic micro-organism, Rhodococcus sp.zw11, was isolated from pharmaceutical wastewater containing hydrogen sulphide (H₂S). The shape, physiological and biochemical characteristics and oxidation capacity of Rhodococcus sp.zw11 were studied, and the effect of inlet concentration and volumetric loading of H₂S on the removal efficiency was evaluated by the biotrickling filter inoculated with Rhodococcus sp.zw11. The results suggested that the optimal temperature of Rhodococcus sp.zw11 (aerobic bacilli, short rod and gram-negative) was from 20°C to 28°C and the optimal pH was from 5.5 to 6.5. The criteria necessary for a scale-up design of the biotrickling filter were established, and pressure drops at the start and end of the experiment were investigated. The optimal inlet loading could be noted as 180 g/m³h, corresponding to H₂S removal efficiency close to 100%. Furthermore, the inoculated biotrickling filter had good ability to resist shock loading, which was a potential industrialisation method to control H₂S emissions.