Hydrogen Sulfide Gas Treatment by a Chemical‐Biological Process: Chemical Absorption and Biological Oxidation Steps

In order to remove high concentrations of hydrogen sulfide (H₂S) gas from anaerobic wastewater treatments in livestock farming, a novel process was evaluated for H₂S gas abatement involving the combination of chemical absorption and biological oxidation processes. In this study, the extensive experiments evaluating the removal efficiency, capacity, and removal characteristics of H₂S gas by the chemical absorption reactor were conducted in a continuous operation. In addition, the effects of initial Fe^2 + concentrations, pH, and glucose concentrations on Fe^2 + oxidation by Thiobacillus ferrooxidans CP9 were also examined. The results showed that the chemical process exhibited high removal efficiencies with H₂S concentrations up to 300 ppm, and nearly no acclimation time was required. The limitation of mass‐transfer was verified as the rate‐determining step in the chemical reaction through model validation. The Fe^2 + production rate was clearly affected by the inlet gas concentration as well as flow rate and a prediction equation of ferrous production was established. The optimal operating conditions for the biological oxidation process were below pH 2.3 and 35°C in which more than 90% Fe^3 + formation ratio was achieved. Interestingly, the optimal glucose concentration in the medium was 0.1%, which favored Fe^2 + oxidation and the growth of T. ferrooxidans CP9.     

Bio-SR工艺去除硫化氢气体的研究

采用Bio-SR工艺,利用铁盐吸收与氧化亚铁硫杆菌的联合作用对H2S进行脱除实验。通过改进微生物的培养条件,减少了83.9%的沉淀量,一定程度上解决了挂膜后生物填料塔易堵塞的问题,保证了填料塔的连续运行。在实验选取工况下,硫化氢脱除率可达到98.4%以上,当吸收液中Fe3+浓度为5.5～6 g/L、H2S进气浓度为1 g/m3、通气量为0.08～0.12 m3/h时效果最佳,反应器可持续高效地运行。此外,对进气浓度、通气量与硫化氢去除率之间的相关性进行了进一步研究,其结果有利于反应器及运行参数的优化设计。     

Hybrid process for heavy metal removal from wastewater sludge.

Bioleaching processes have been demonstrated to be effective technologies in removing heavy metals from wastewater sludge, but long hydraulic retention times are typically required to operate these bioprocesses. A hybrid process (coupling biological and chemical processes) has been explored in laboratory pilot-scale experiments for heavy metals (cadmium [Cd], copper [Cu], chromium [Cr], and zinc [Zn]) removal from three types of sludge (primary sludge, secondary activated sludge, and a mixture of primary and secondary sludge). The hybrid process consisted of producing a concentrate ferric ion solution followed by chemical treatment of sludges. Ferric iron solution was produced biologically via oxidation of ferrous iron by A. ferrooxidans in a continuous-flow stirred tank (5.2 L) reactor (CSTR). Wastewater sludge filtrate (WSF) containing nutrients (phosphorus and nitrogen) has been used as culture media to support the growth and activity of indigenous iron-oxidizing bacteria. Results showed that total organic carbon (TOC) concentrations of the culture media in excess of 235 mg/L were found to be inhibitory to bacterial growth. The oxidation rate increased as ferrous iron concentrations ranged from 10 to 40 g Fe2+/L. The percentage of ferrous iron (Fe2+) oxidized to ferric iron (Fe3+) increased as the hydraulic retention time (HRT) increased from 12 to 48 h. Successful and complete Fe2+ oxidation was recorded at a HRT of 48 h using 10 g Fe2+/L. Subsequently, ferric ion solution produced by A. ferrooxidans in sludge filtrate was used to solubilize heavy metals contained in wastewater sludge. The best solubilization was obtained with a mixture of primary and secondary sludge, demonstrating a removal efficiency of 63, 71, 49, and 80% for Cd, Cu, Cr, and Zn, respectively.     

A comparative study of the removal of 3-indolebutyric acid using advanced oxidation processes

In this study, advanced oxidation technologies, namely Fenton Process (FP), Fenton-Like Process (FLP), ozonation (O3) and O3/H2O2 processes, were applied to synthetic wastewater containing 3-indolebutyric acid (IBA). The effectiveness of each process was investigated at different pH values, Fe(+2), Fe(+3), O3 and H2O2 concentrations with respect to the removal efficiencies for chemical oxygen demand (COD) and total organic carbon (TOC). The best removal efficiencies were seen at pH 3 and 2 mM Fe concentration in both FP and FLP, in which the optimum H2O2 concentrations were 6 mM for FP and 10 mM for FLP. Optimum process conditions were pH 12 for the O3 process, pH 9 for the O3/H2O2 process and 1:1 O3/H2O2 molar ratio. The highest COD removal efficiency was 86 percent, obtained in the O3/H2O2 process and the highest TOC removal efficiency was obtained at 77 percent in the FP.     

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.     

Chemical absorption process for degradation of VOC gas using heterogeneous gas-liquid photocatalytic oxidation: toluene degradation by photo-Fenton reaction

A novel process for degradation of toluene in the gas-phase using heterogeneous gas-liquid photocatalytic oxidation has been developed. The degradation of toluene gas by photo-Fenton reaction in the liquid-phase has experimentally examined. The photo-Fenton reaction in the liquid-phase could improve the overall toluene absorption rate by increasing the driving force for mass transfer and as a result enhance the removal of toluene in the exhaust gas. The toluene concentrations in the inlet gas were varied in the range from 0.0968 to 8.69gm(-3) with initial hydrogen peroxide concentration of 400mgl(-1) and Fe dose of 5.0mgl(-1). It was found that toluene in the inlet gas was almost completely dissolved into water and degraded in the liquid-phase for the inlet toluene gas concentration of less than 0.42gm(-3). The dynamic process of toluene gas degradation by the photo-Fenton reaction providing information for reaction kinetics and mass transfer rate was examined. Toluene removal kinetic analysis indicated that photo-Fenton degradation was significantly affected by H(2)O(2) concentration. The experimental results were satisfactorily described by the predictions simulated using the simplified tanks-in-series model combined with toluene removal kinetic analysis. The present results showed that the proposed chemical absorption process using the photo-Fenton heterogeneous gas-liquid photocatalytic oxidation is very effective for degradation of volatile organic gases.     

神经节苷脂生产废水处理技术研究

针对神经节苷脂生产废水蛋白质含量高的特点,研究了等电点沉淀或混凝沉降预处理、厌氧好氧生物处理、化学沉淀和类Fenton氧化后处理组合工艺处理神经节苷脂生产废水的技术。结果表明,神经节苷脂生产废水的等电点在pH=2.2左右,通过等电点沉淀可去除30%以上的COD,但等电点时蛋白质的沉淀速度非常慢;用聚合硫酸铁对神经节苷脂生产废水进行混凝预处理的最适工艺条件是：pH=7～7.5,聚合硫酸铁用量＝500～750 mg/L。在优化条件下,混凝预处理可以使神经节苷脂生产废水的COD从27 000 mg/L左右降到13 000 mg/L左右。混凝预处理后的神经节苷脂生产废水经48 h厌氧和84 h好氧生物处理,COD值进一步下降到600 mg/L左右。然后向每升生化出水中加入2～3 mmol Fe³⁺,通过化学沉淀作用除去其中的磷酸盐,过量的Fe³⁺作为后续类Fenton氧化的催化剂。当H₂O₂(30％)用量为2～3 mL/L时,最终出水的COD值可以达到国家一级排放标准。     

Degradation of the pharmaceutical metronidazole via UV, Fenton and photo-Fenton processes

Degradation rates and removal efficiencies of Metronidazole using UV, UV/H2O2, H2O2/Fe2+, and UV/H2O2/Fe2+ were studied in de-ionized water. The four different oxidation processes were compared for the removal kinetics of the antimicrobial pharmaceutical Metronidazole. It was found that the degradation of Metronidazole by UV and UV/H2O2 exhibited pseudo-first order reaction kinetics. By applying H2O2/Fe2+, and UV/H2O2/Fe2+ the degradation kinetics followed a second order behavior. The quantum yields for direct photolysis, measured at 254 nm and 200-400 nm, were 0.0033 and 0.0080 mol E(-1), respectively. Increasing the concentrations of hydrogen peroxide promoted the oxidation rate by UV/ H2O2. Adding more ferrous ions enhanced the oxidation rate for the H2O2/Fe2+ and UV/H2O2/Fe2+ processes. The major advantages and disadvantages of each process and the complexity of comparing the various advanced oxidation processes on an equal basis are discussed.     

Decolorization and degradation of H-acid and other dyes using ferrous-hydrogen peroxide system

In this study, advanced oxidation process utilizing Fenton's reaction was investigated for the decolorization and degradation of two commercial dyes viz., Red M5B, Blue MR and H-acid, a dye intermediate used in chemical industries for the synthesis of direct, reactive and azo dyes. Effect of Fe2 +, H2O2, pH, and contact time on the degradation of the dyes was studied. Maximum color and COD removal was obtained for Red MSB, H-acid and Blue MR at 10-25 mg/l of Fe2+ dose and 400-500 mg/l of H2O2 dose at pH 3.0. The initial oxidation reaction was found to fit into first order rate kinetics and the rate of oxidation of H-acid was higher than the other dyes. Release of chloride and sulfate from the Fenton's treated Red M5B dye and sulfate from H-acid and Blue MR indicates that the dye degradation proceeds through cleavage of the substituent group.     

Kinetics and stoichiometry of aerobic sulfide oxidation in wastewater from sewers-effects of pH and temperature.

Kinetics and stoichiometry of aerobic chemical and biological sulfide oxidation in wastewater from sewer networks were studied. In this respect, the effects of temperature and pH were investigated in the ranges 10 to 20 degrees C and 5 to 9, respectively. The temperature dependency of sulfide oxidation kinetics was described using an Arrhenius relationship. The effect of pH on the rate of chemical sulfide oxidation is related to the dissociation of hydrogen sulfide (H2S) to hydrogen sulfide ion (HS(-)), with HS(-) being more readily oxidized than H2S. Biological sulfide oxidation exhibited the highest rates at ambient wastewater pH, and the reaction was inhibited at both low and high pH values. Chemical sulfide oxidation was found to produce thiosulfate and sulfate, while elemental sulfur was the main product of biological sulfide oxidation. Based on the investigations, general rate equations and stoichiometric constants were determined, enabling the processes to be incorporated to conceptual sewer process models.     

混凝-Fenton氧化-Fe0还原预处理高浓度硝基苯生产废水

采用混凝-Fenton氧化-Fe0还原工艺预处理高浓度硝基苯废水,考察各反应阶段硝基苯去除效果及影响因素。研究表明,聚铁混凝性能优于聚铝;初始COD为17 350 mg/L、硝基苯浓度为10 050 mg/L的废水,在pH=4,聚铁投加浓度3 300 mg/L时,COD和硝基苯去除率分别为63%和62%;混凝沉降后的上清液用Fenton试剂氧化,可在较宽pH(3～6)范围内降解硝基苯,当H2O2(30%)浓度为6 000 mg/L,Fe2+浓度为168 mg/L时,氧化效率最高;聚铁混凝-Fenton氧化后的出水用Fe0还原,最佳还原条件为:pH=3,Fe0浓度1 500 mg/L。原水经聚铁混凝-Fenton氧化-Fe0还原后,COD和硝基苯总去除率分别达90%和98%,总药剂成本约12.4元/t。处理后废水硝基苯浓度为168 mg/L,适宜进行后续的厌氧-好氧生物处理。     

Transformation characteristics of refractory pollutants in plugboard wastewater by an optimal electrocoagulation and electro-Fenton process

The treatment of the plugboard wastewater was performed by an optimal electrocoagulation and electro-Fenton. The organic components with suspended fractions accounting for 30% COD were preferably removed via electrocoagulation at initial 5 min. In contrast, the removal efficiency was increased to 76% with the addition of H(2)O(2). The electrogenerated Fe(2+) reacts with H(2)O(2) and leads to the generation of (·)OH, which is responsible for the higher COD removal. However, overdosage H(2)O(2) will consume (·)OH generated in the electro-Fenton process and lead to the low COD removal. The COD removal efficiency decreased with the increased pH. The concentration of Fe(2+) ions was dependent on the solution pH, H(2)O(2) dosage and current density. The changes of organic characteristics in coagulation and oxidation process were differenced and evaluated using gel permeation chromatography, fluorescence excitation-emission scans and Fourier transform infrared spectroscopy. The fraction of the wastewater with aromatic structure and large molecular weight was decomposed into aliphatic structure and small molecular weight fraction in the electro-Fenton process.     

序批式工艺制备生物聚合硫酸铁混凝剂

本实验研究了序批式工艺(SBR)制备生物聚合铁混凝剂过程中主要影响因素(接种微生物浓度、起始亚铁离子浓度)对亚铁离子氧化速率的影响。研究结果显示,在受试实验条件内,较高的接种微生物浓度和较低的起始Fe2+浓度有利于Fe2+氧化,Fe2+浓度变化与反应时间呈线性关系;当起始Fe2+浓度为20 g/L,接种细菌浓度约为8×108个/mL时,Fe2+氧化速率最大,最大值可达到0.375 g/(L.h)。在反应过程中生成了少量黄色沉淀,经傅里叶变换红外光谱分析后确定其主要成分为黄钾铁矾。合成的生物聚合硫酸铁经过干化后各项指标均符合《水处理剂聚合硫酸铁》(GB 14591-2006)之规定。对比实验表明,自制生物聚合硫酸铁海水混凝时性能优于实验所选品牌的商业产品。     

Fe^2＋—H2O2氧化法处理氨基J酸工业废水的研究

用Ｆｅ＾２＋－Ｈ２Ｏ２氧化法处理氨基Ｊ酸工业废水。结果表明,当溶液ｐＨ＝１－３,Ｈ２Ｏ２和Ｆｅ＾２＋用量分别为Ｈ２Ｏ２：Ｆｅ＾２＋１０：１,Ｈ２Ｏ２：ＣＯＤＣｒ＝２ｇ：ｇ时,Ｊ酸废水的ＣＯＤＣｒ去除率达６６．７％,氨基去除率达６８．４％。处理后的废水ＢＯＤ５／ＣＯＤＣｒ＝０．５,已达到生化处理的要求。该法可作为氨基Ｊ酸废水的预处理方法。     

Effect of solution pH on SO2, NO(x), and Hg removal from simulated coal combustion flue gas in an oxidant-enhanced wet scrubber

This paper presents a study on the simultaneous removal of SO2, NO(x) and Hg (both Hg0 and Hg2+) from a simulated flue gas by oxidant injection in a bench-simulated wet limestone scrubber for a wide range of slurry pH. The slurry pH strongly influenced the chemical mechanism in the scrubber and, therefore, affected pollutant removal. This paper also examines the potential ClO2(gas) reemission from a developed multipollutant scrubber at different slurry pHs. To better understand the chemical mechanisms at each slurry pH and to apply a mass balance to the process, detailed product ion analyses were performed for all experiments. Ion analysis covered three different chlorine species (chlorite, chloride, chlorate), sulfate, nitrite and nitrate. Different NO(x) removal efficiencies and mechanisms were found in acidic and alkaline pHs in the multipollutant scrubber. The acidic solution was favorable for NO and Hg0 oxidation, but increasing the slurry pH above 7.0 was disadvantageous for NO and Hg oxidation/removal. However the rate of NO(x) absorption (by percentage) was higher for the alkaline solution.     

Effect of pH on the aggregation of a gray humic acid in colloidal and solid states

The potential of triethylenetetramine (TETA) to inhibit the oxidation of three pyrrhotites, Garson, McCreedy and Po-97 has been studied systematically and confirmed by comparing the release of Fe and SO4(2-) from samples with and without coating treatment. Each sample, original or coated by TETA, was exposed to oxygen, 1 x 10(-3) M FeCl3, and Acidithiobacillus ferrooxidans, respectively, for specific oxidation periods. Both abiotic and biotic oxidation of samples treated by this passivating agent has been reduced significantly in this study. Under the aerobic condition, lower concentrations of ferric, total Fe or SO4(2-) were obtained from the coated samples than those from the uncoated samples. In the presence of 1 x 10(-3) M FeCl3 at 30 degrees C, TETA was able to reduce oxidation rates of Garson, McCreedy and Po-97 by 83%, 79%, and 81% (based on Fe release), respectively. A higher pH, lower Eh, and lower concentrations of total Fe and SO4(2-) were also observed in the biotic oxidation of coated Garson by Acidithiobacillus ferrooxidans. The protection of pyrrhotite surface from oxidant attack by TETA barrier and the alkaline property of this coating agent can be used to interpret the inhibition of oxidation.     

超声-Fenton法处理偶氮染料橙黄II的研究

以偶氮染料橙黄II为研究对象 ,考察了Fenton反应在超声辐射条件下 ,pH值、H2 O2 浓度、Fe2 + 离子浓度对COD去除率的影响。实验结果表明 ,超声对Fenton试剂处理偶氮染料橙黄II具有强化作用。超声条件下 ,当染料浓度为10 0mg/L、pH为 3.0、Fe2 + 离子浓度为 10mg/L、H2 O2 浓度为 4 0 0mg/L时 ,反应 90min ,COD去除率最高可达 93%。     

Photochemical degradation and mineralization of 4-chlorophenol

INTENTION, GOAL, SCOPE, BACKGROUND: Since the intermediate products of some compounds can be more toxic and/or refractory than the original compund itself, the development of innovative oxidation technologies which are capable of transforming such compounds into harmless end products, is gaining more importance every day. Advanced oxidation processes are one of these technologies. However, it is necessary to optimize the reaction conditions for these technologies in order to be cost-effective. OBJECTIVE: The main objectives of this study were to see if complete mineralization of 4-chlorophenol with AOPs was possible using low pressure mercury vapour lamps, to make a comparison of different AOPs, to observe the effect of the existence of other ions on degradation efficiency and to optimize reaction conditions. METHODS: In this study, photochemical advanced oxidation processes (AOPs) utilizing the combinations of UV, UV/H2O2 and UV/H2O2/Fe2+ (photo-Fenton process) were investigated in labscale experiments for the degradation and mineralization of 4-chlorophenol. Evaluations were based on the reduction of 4-chlorophenol and total organic carbon. The major parameters investigated were the initial 4-chlorophenol concentration, pH, hydrogen peroxide and iron doses and the effect of the presence of radical scavengers. RESULTS AND DISCUSSION: It was observed that the 4-chlorophenol degradation efficiency decreased with increasing concentration and was independent of the initial solution pH in the UV process. 4-chlorophenol oxidation efficiency for an initial concentration of 100 mgl(-1) was around 89% after 300 min of irradiation in the UV process and no mineralization was achieved. The efficiency increased to > 99% with the UV/H2O2 process in 60 min of irradiation, although mineralization efficiency was still around 75% after 300 min of reaction time. Although the H2O2/4-CP molar ratio was kept constant, increasing initial 4-chlorophenol concentration decreased the treatment efficiency. It was observed that basic pHs were favourable in the UV/H2O2 process. The results showed that the photo-Fenton process was the most effective treatment process under acidic conditions. Complete disappearance of 100 mgl(-1) of 4-chlorophenol was achieved in 2.5 min and almost complete mineralization (96%) was also possible after only 45 min of irradiation. The efficiency was negatively affected from H2O2 in the UV/H2O2 process and Fe2+ in the photo-Fenton process over a certain concentration. The highest negative effect was observed with solutions containing PO4 triple ions. Required reaction times for complete disappearance of 100 mgl(-1) 4-chlorophenol increased from 2.5 min for an ion-free solution to 30 min for solutions containing 100 mgl(-1) PO4 triple ion and from 45 min to more than 240 min for complete mineralization. The photodegradation of 4-chlorophenol was found to follow the first-order law. CONCLUSION: The results of this study showed that UV irradiation alone can degrade 4-CP, although at very slow rates, but cannot mineralize the compound. The addition of hydrogen peroxide to the system, the so-called UV/H2O2 process, significantly enhances the 4-CP degradation rate, but still requires relatively long reaction periods for complete mineralization. The photo-Fenton process, the combination of homogeneous systems of UV/H2O2/Fe2+ compounds, produces the highest photochemical elimination rate of 4-CP and complete mineralization is possible to achieve in quite shorter reaction periods when compared with the UV/H2O2 process. RECOMMENDATIONS AND OUTLOOK: It is more cost effective to use these processes for only purposes such as toxicity reduction, enhancement of biodegradability, decolorization and micropollutant removal. However the most important point is the optimization of the reaction conditions for the process of concern. In such a case, AOPs can be used in combination with a biological treatment systems as a pre- or post treatment unit providing the cheapest treatment option. The AOP applied, for instance, can be used for toxicity reduction and the biological unit for chemical oxygen demand (COD) removal.     

氧化亚铁硫杆菌的筛选、生长特性及其橡胶再生研究

从大西洋底死火山口土壤中筛选出一株硫杆菌,经16S rDNA鉴定为氧化亚铁硫杆菌。研究了初始底物Fe2+浓度,初始pH,接种量对其生长的影响,确定了其最佳的生长的条件:在30℃、170 r/min条件下,最适底物Fe2+浓度为9 g/L,最佳初始pH为2.5,最适接种量为10%(体积分数)。探讨了氧化亚铁硫杆菌对天然硫化橡胶的脱硫再生,橡胶的SEM分析、FTIR图谱及EDS图谱研究表明氧化亚铁硫杆菌对硫化胶粉的硫交联键有断裂或转化作用,脱硫率达52.6%,氧化亚铁硫杆菌对天然橡胶具有一定的再生作用。     

连续式生物吸收工艺脱除二氧化硫

运用连续式生物吸收处理工艺,以废糖蜜发酵液作为碳源进行了微生物法去除SO2气体的研究,在简单粗放的实验条件下,研究了脱硫脱硫弧菌对较大气量SO2气体的去除效果,并对产物H2S在第二级生物反应器中的去除率进行了测定。实验结果表明,随着进气量由0.18 m3/h增大至5 m3/h,脱硫率会降低,但是随之提高搅拌速度和补料速度后,脱硫率又恢复到较高水平,当搅拌速度为590 r/min时,5 L生物反应液可以处理5 m3/h的SO2气体,1#反应器SO2去除率和2#反应器H2S去除率分别达到92%和98%以上。在气量增至5 m3/h时,1#和2#反应器补料流速分别为175 mL/h和200 mL/h时,没有亚硫酸盐和硫化物的积累,pH值和菌体浓度稳定,系统运行良好。