Online oxygen control for sulfide oxidation in anaerobic treatment of high-sulfate wastewater.

A new technique for sulfide control was investigated in an upflow-anaerobic filter (UAF) treating high-strength, sulfate-rich wastewater. The technique used periodic oxygen injection using oxidation-reduction potential (ORP) as a controlling parameter to regulate oxygen injection. The UAF was operated at a constant influent total-organic carbon of 6740 mg/L but with different influent sulfates of 1000, 3000, and 6000 mg/L. At 1000 and 3000 mg/L influent sulfates, the produced sulfide did not impose any inhibition to methane-producing bacteria (MPB). However, at 6000 mg/L influent sulfate, the produced dissolved sulfide of 804 mg S/L (free sulfide = 280 mg S/L) severely inhibited the methanogenesis, but not the sulfidogenesis. Upon oxygen injection at elevated ORP of -265 mV, sulfides were almost completely eliminated with a concomitant improvement in methane yield by 46%. If oxygenation was excessive because of an oversetting of ORP, the excess oxygen could be used rapidly by facultative heterotrophs, thereby protecting the MPB from oxygen stress. Regarding online sulfide oxidation, it was found that the biogas and injected oxygen needed to pass through an aqueous layer containing trace metals, which were found to have a significant catalytic effect on abiotic sulfide oxidation.     

Inhibition of sulfide generation in a reclaimed wastewater pipe by nitrate dosage and denitrification kinetics.

Sulfide generation should be avoided during wastewater transportation. The efficiency of nitrate dosing for the inhibition of sulfide generation was evaluated during reclaimed wastewater transport with two nitrate doses, 2.5 and 5 mg/L nitrate-nitrogen (NO3-N). A calcium nitrate [Ca(NO3)2] solution was injected at the beginning of the 61-km-long gravity pipe, which is part of the Reclaimed Wastewater Reuse System of South Tenerife (Spain). During transportation, after dissolved oxygen depletion, a denitrification process took place. With the 5 mg/L NO3-N dose, nitrate was not completely removed at the end of the pipe, whereas with 2.5 mg/L NO3-N, a complete denitrification was achieved. Sulfide generation was completely inhibited with the 5 mg/L dose. However, with 2.5 mg/L, sulfide generation was not completely inhibited but delayed and minimized to a great extent. Denitrification was stoichiometrically limited by the availability in biodegradable matter. An empirical equation enables one to predict the nitrate concentration.     

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。     

Prevention of sulfide oxidation in waste rock by the addition of lime kiln dust

During the operation of a mine, waste rock is often deposited in heaps and usually left under ambient conditions allowing sulfides to oxidize. To focus on waste rock management for preventing acid rock drainage (ARD) formation rather than ARD treatment could avoid its generation and reduce lime consumption, costs, and sludge treatment. Leachates from 10 L laboratory test cells containing sulfide-rich (>?60% pyrite) waste rock with and without the addition of lime kiln dust (LKD) (5 wt.%) were compared to each other to evaluate the LKD’s ability to maintain near neutral pH and reduce the sulfide oxidation. Leaching of solely waste rock generated an acidic leachate (pH?<?1.3) with high concentrations of As (21 mg/L), Cu (20 mg/L), Fe (18 g/L), Mn (45 mg/L), Pb (856 μg/L), Sb (967 μg/L), S (17 g/L), and Zn (23 mg/L). Conversely, the addition of 5 wt.% LKD generated and maintained a near neutral pH along with decreasing of metal and metalloid concentrations by more than 99.9%. Decreased concentrations were most pronounced for As, Cu, Pb, and Zn while S was relatively high (100 mg/L) but decreasing throughout the time of leaching. The results from sequential extraction combined with element release, geochemical calculations, and Raman analysis suggest that S concentrations decreased due to decreasing sulfide oxidation rate, which led to gypsum dissolution. The result from this study shows that a limited amount of LKD, corresponding to 4% of the net neutralizing potential of the waste rock, can prevent the acceleration of sulfide oxidation and subsequent release of sulfate, metals, and metalloids but the quantity and long-term stability of secondary minerals formed needs to be evaluated and understood before this method can be applied at a larger scale.

     

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.     

纳米铁-真养产碱杆菌柱实验去除硝酸盐

建立柱实验装置,探讨了反应柱中填加介质、硝酸盐的初始浓度及不同过水流速时硝酸盐的去除效果及产物的生成情况。4种不同材料,纳米铁、真养产碱杆菌、纳米铁与真养产碱杆菌简单混合体、纳米铁与真养产碱杆菌驯化培养5 d的复合体,分别与初始浓度为65 mg/L硝酸盐溶液反应。结果表明,经培养5 d的纳米铁-真养产碱杆菌复合体对硝酸盐的去除效果最佳,去除率可达到75%,且氨氮的生成量仅为2.99 mg/L;硝酸盐初始浓度分别为32、65和95 mg/L时,32mg/L的体系中硝酸盐的降解效果最好,去除率达78.9%且亚硝酸盐及氨氮的生成量分别为2.34 mg/L和2.89 mg/L,均低于另外2组;溶液流速为6.0 cm/h时,经驯化培养的纳米铁-真养产碱杆菌对硝酸盐的去除率达77%,当控制流速降至2.4cm/h时,亚硝酸盐氮的生成量降至0.34 mg/L。     

电化学脱硝过程参数的响应曲面优化研究

以Ti/IrO2-TiO2-RuO2为阳极,Cu/Zn合金电极为阴极,在无隔膜电解池中对这一新构造电极对的脱硝氮性能进行了研究。为了有效结合阴极硝氮还原能力和阳极氧化能力,采用响应曲面法中的Box-Behnken设计优化了对电化学脱硝过程有显著影响的4个重要因素:氯化钠含量、电流密度、pH和初始硝氮浓度。优化结果表明,相对于pH和初始硝氮浓度,氯化钠含量和电流密度对脱硝性能影响更大,而阴极硝氮还原性能主要受初始硝氮浓度、pH的影响。以6 h内电极对脱氮百分率为响应量,优化得最佳电化学脱硝过程参数为:氯化钠含量,1 g/L;电流密度,24.99 mA/cm2;pH,1.81;初始硝氮浓度100 mg/L。在此实验条件下,6 h内电极对脱氮百分率预测值为99.84%。通过3次重复验证实验,确认实际6 h内电极对脱氮百分率为91.34%。预测值与实测值两者相差不大,由此可知,Box-Behnken设计是一种优化电化学脱氮实验参数的有效方法,经过优化后的电极对具有较佳的脱氮效率。     

Elimination of phenol and aromatic compounds by zero valent iron and EDTA at low temperature and atmospheric pressure

This work deals with a new abiotic oxidation process designed as a suitable pre-treatment step within a biological depuration of wastewater containing phenol or its derivatives (o-cresol, 2-chlorophenol and p-nitrophenol) or aniline. The reaction was carried out in a stirred tank reactor at 20 degrees C and atmospheric pressure in presence of the organic compound, 150mgl(-1), zero valent iron particles (10g), ethylenediamine tetraacetic acid (EDTA, 101mgl(-1)) and air. The experimental results show that 85% of phenol conversion can be achieved after 360min. 2-Chlorophenol was found to be more easily degradable and it is completely eliminated after 300min. The oxidation of o-cresol and aniline behaved more closely to phenol obtaining after 360min 70% and 68% of conversion respectively. p-Nitrophenol was a very refractory compound, giving only 28% of conversion after 360min. Moreover, the influence of some operating variables was studied over the following ranges: temperature from 20 to 50 degrees C, initial phenol concentration from 150 to 1000mgl(-1), EDTA concentration from 50 to 200mgl(-1) and iron particles from 5 to 20g. As expected, temperature strongly enhances phenol conversion. Also, an increase of the catalyst to phenol ratio or the iron or EDTA to phenol ratio improves the reaction rate. A preliminary kinetic analysis of the data shown that the rate of phenol disappearance is not first order with respect to the phenol.     

Kinetics of chemical decolorization of the azo dye C.I. Reactive Orange 96 by sulfide

The mechanism of decolorization of azo dyes based on the extracellular chemical reduction with sulfide (H2S, HS-, S2-) was postulated for sulfate reducing environments. To design technical decolorization processes of textile wastewater treatment with sulfide produced by sulfate reducing bacteria (SRB), kinetics is of great significance. Batch experiments were made in order to investigate the kinetics of abiotic decolorization of the reactive mono-azo dye C.I. Reactive Orange 96 (RO 96) with sulfide, with varying pH. The decolorization of RO 96 by sulfide under the exclusion of O2 corresponded to first-order kinetics with respect to both dye and sulfide concentration. The decolorization of RO 96 with sulfide at neutral pH (7.1) was advantageous compared with that at pH for 4.1, 6.3, and 6.5. This is attributed to an increase in the fraction of HS- of total sulfide species at neutral pH. The rate constants k for the decolorization at 37 degrees C were obtained as 0.01 for pH = 4.1, 0.06 for pH = 6.3, 0.08 for pH = 6.5, and 0.09 for pH = 7.1 in mM(-1) min(-1). The high rate constants for sulfide at pH 6.5-7.1 support that the decolorization through SRB (i.e. by bio-sulfide) can be effective in anaerobic bacterial systems with sulfate.     

混合硫酸盐还原菌代谢过程的影响因素

采用间歇实验,研究不同初始pH、Fe2+投加量、COD/SO24-及NO3-/SO24-比值等因素对SRB还原硫酸盐效果与速率的影响。实验结果表明:中性条件下(pH=7),硫酸盐的去除效果最佳,去除率达到84.66%,还原速率为15.07 mg/(L.h),在初始pH为4～9的范围内,体系具有较好的缓冲能力;当COD/SO24-比值为3时,反应209 h,硫酸盐去除率为85.33%,还原速率为8.16 mg/(L.h),随着反应的进行,体系的pH趋于中性;当溶液中有亚铁离子存在,且浓度为0～200 mg/L时可促进硫酸盐还原菌的生长,提高其对硫酸盐的去除率;NO3-对硫酸盐的还原有明显的抑制作用。     

Pressurized CO2/zero valent iron system for nitrate removal

A fluidized zero valent iron (ZVI) reactor pressurized by CO(2) gas for controlling pH was employed for nitrate reduction. The proposed CO(2) pressurized system potentially has advantages of using less CO(2) gas and reaching equilibrium pH faster than CO(2)-bubbled system. However, due to weak acid nature of carbonic acid, system pH gradually increased with increasing oxidation of ZVI and reduction of nitrate. As pH increased with progress of reaction, nitrate removal rate decreased continuously. The results indicate that nitrate removal efficiency increases with increasing initial ZVI dosage but reaches plateau at ZVI doses of higher than 8.25gl(-1), and initial nitrate concentration up to 100mg l(-1) as N has minimal impact on the removal efficiency. Unlike the fluidized system with pH control by strong acid reported in our pervious study, near 100% of nitrogen recovery was observed in the current process, indicating that nitrate reduction by ZVI with different pH controlled mechanisms will have different reaction routes.     

Simultaneous Cr(VI) reduction and phenol degradation using Stenotrophomonas sp. isolated from tannery effluent contaminated soil

This study presents simultaneous hexavalent chromium (Cr(VI)) reduction and phenol degradation using Stenotrophomonas sp., isolated from tannery effluent contaminated soil. Phenol was used as the sole carbon and energy source for Cr(VI) reduction. The optimization of different operating parameters was done using Placket–Burman design (PBD) and Box–Behnken design (BBD). The significant operating variables identified by PBD were initial Cr(VI) and phenol concentration, pH, temperature, and reaction time. These variables were optimized by a three-level BBD and the optimum initial Cr(VI) concentration, initial phenol concentration, pH, temperature, and reaction time obtained were 16.59 mg/l, 200.05 mg/l, 7.38, 31.96 °C and 4.07 days, respectively. Under the optimum conditions, 81.27 % Cr(VI) reduction and 100 % phenol degradation were observed experimentally. The results concluded that the Stenotrophomonas sp. could be used to decontaminate the effluents containing Cr(VI) and phenol effectively.     

硫化物矿山尾矿生物氧化作用的抑制研究

硫化物矿山尾矿的风化、氧化会对周围环境产生危害,研究表明,以氧化亚铁硫杆菌为代表的嗜酸氧化菌起了非常重要的作用。本研究以从广东韶关大宝山尾矿分离得到的一株氧化亚铁硫杆菌作为实验菌株,添加不同剂量的杀菌剂,分析了杀菌剂对溶液pH、Eh值的影响,及杀菌剂的Fe2+氧化抑制率和最佳使用浓度。结果显示:实验用杀菌剂SDS和CTAB能有效地抑制金属硫化物尾矿的生物氧化和酸化:ρ(SDS)为30 mg/L时Fe2+的氧化抑制率达到82.83%;ρ(CTAB)为5 mg/L时Fe2+的氧化抑制率达到80.84%,添加了杀菌剂的溶液pH、Eh基本保持初始值不变,表明杀菌剂的使用可以控制金属硫化物尾矿的酸化污染。     

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.     

接种物对厌氧同步脱硫反硝化特性的影响实验研究

分别以厌氧污泥、脱氮硫杆菌菌悬液和厌氧污泥并添加脱氮硫杆菌菌悬液为接种物,以硫化物和硝酸盐为进水基质,考察不同接种物条件下,各反应器的硫化物氧化特性、反硝化特性、生化反应机理及微生物特性。结果表明,在无菌条件下,硫化物不能被硝酸盐化学氧化。接种脱氮硫杆菌菌悬液的2#反应器的硫氧化速率为1.98 g S/(m3.h),停留24 h硫化物的去除率高达97%,脱硫能力最强,该接种条件下以硝酸盐氧化硫化物为主反应,优势菌为杆菌,进水的NO3--N/S应控制在0.4以下,可以实现高效生物脱硫。接种厌氧污泥的1#和3#反应器的脱氮效果比2#反应器好,停留时间为24 h时,硝酸盐的平均去除率为96%。单独接种厌氧污泥的1#反应器的硫氧化速率为1.78 g S/(m3.h),其优势菌为球菌,该接种条件下以硝酸盐氧化硫化物和硝酸盐氧化单质硫为主反应,进水的NO3--N/S应控制在0.8左右。以厌氧污泥联合脱氮硫杆菌为接种物时,硫氧化速率为1.71 g S/(m3.h),反应器以硝酸盐氧化硫化物、硝酸盐氧化单质硫以及异养反硝化为主反应,驯化后优势菌为球形、卵圆形和短杆状,应控制进水NO3--N/S为1.2,可以实现同步脱硫反硝化,该工艺既可以用于含硫废水的处理,也可以用于C/N低的硝酸盐废水的处理。     

An assessment of the suitable operating conditions for the CeO2/gamma-Al2O3 catalyzed wet air oxidation of phenol

It has been shown that the CeO2/gamma-Al2O3 catalyst is a feasible alternative to CeO2 for the catalytic wet air oxidation (CWAO) of phenol because it remains an effective catalyst and yet is cheaper to prepare. In this study, we found that the optimal cerium content in the CeO2/gamma-Al2O3 catalyst was 20 wt.%, regardless of catalyst loading. Furthermore, at 180 degrees C, with a phenol concentration of 1000 mg l(-1), and an O2 partial pressure of 1.0M Pa or 1.5M Pa, the optimal catalyst loading was 3.0 gl (-1). The efficacy of CWAO of phenol improved with O2 partial pressure, although the effects of O2 pressure were more significant between 0.5 MPa and 1.5 MPa than between 1.5 MPa and 2.0 MPa. After 2 h of reaction, approximately 100% phenol conversion and 80% total organic carbon (TOC) removal was recorded at 180 degrees C, 1000 mg l(-1) of phenol and 3.0 g l(-1) of catalyst. Because these percentages subsequently leveled off, it is suggested that 2 h is a suitable time over which to run the reaction. The efficacy of CWAO of phenol decreased as initial phenol concentration was raised (from 400 to 2500 mg l(-1)), with the exception of phenol conversion after about 2 h, for which 400 mg l(-1) produced the lowest phenol conversion figure. Higher phenol concentrations require both catalyst loading and O2 partial pressure to be increased to maintain high performance. For example, for 2000 mg l(-1) and 2500 mg l(-1) phenol, nearly 100% phenol conversion and 90% TOC removal after 4 h of reaction at 180 degrees C required 4.0 g l(-1) of catalyst and 2.0 MPa.     

The effect of emergent macrophytes on the dynamics of sulfur species and trace metals in wetland sediments

This study focuses on the effect of plants on the biogeochemistry of sulfur species and the mobility of heavy metals in wetland sediments. Results showed that, in the presence of plants, sediments had elevated sulfate concentrations in the rhizosphere during the growing season, ranging from 0.2 to 6.20 mmol L(-1), whereas only a small difference in the sulfate profiles between vegetated and non-vegetated sediments was observed during senescence. Based on the sulfate concentration increase, the oxygen release rate from the roots to achieve the corresponding oxidation of sulfide was estimated as 0.85 g m(-2) day(-1). Evapotranspiration-induced advection is a major contributor to the transport of sulfate from the water column into the sediments, and also allows dissolved trace metals (i.e. Cd, Pb, and Zn) to be transported into the sediments and react with the acid volatile sulfide pool, resulting in the immobilization of trace metals in these sediments.     

Effect of high influent sulfate on anaerobic wastewater treatment.

A laboratory-scale study was conducted using a completely mixed reactor with a constant influent-total-organic carbon (TOC) of 3750 mg/L to evaluate the effect of increasing influent-sulfate levels on anaerobic-treatment performance. The sulfate levels were increased stepwise from 333 to 666, 1000, 1333 and 1666 mg S/L. The results showed that an elevation of influent sulfate actually increased the TOC removal efficiency as long as the produced sulfide level did not induce toxicity. At 1333 mg S/L influent sulfate, the produced dissolved sulfide was 613 mg S/L (free sulfide = 228 mg S/L), which started to impose toxicity to the methane-producing bacteria (MPB). It was also found that the percent electron flow to the sulfate-reducing pathway increased with the increasing influent sulfate, but the direction toward the methanogenesis was correspondingly reduced. Nevertheless, under the experimental conditions tested, the majority of the influent organics was still degraded through the methanogenic pathway. Through this study, an oxidation-reduction-potential (ORP)-based oxygenation process was developed for online oxidation of sulfide in recirculating biogas. With controlled oxygen injection to raise the reactor's ORP by 25 mV, the residual sulfide in the reactor was almost totally eliminated. In case of over oxygenation, any excess oxygen was quickly consumed by the facultative organisms in the reactor, thereby imposing no toxicity to the MPB.     

昆明市污水排水系统产甲烷规律的模拟实验研究

通过对昆明市餐饮和居民生活污水厌氧模拟实验研究,初步探讨生活污水中CH4的产生规律,实验结果表明,在自然条件下,餐饮和居民生活污水中产生的甲烷浓度最大值分别为1.63 mg/L和3.82 mg/L。并且将COD、硫酸盐、硫化物、TN的浓度变化与甲烷浓度变化进行Pearson简单相关性分析,结果表明,1/COD、COD/硫酸盐和1/TN与甲烷在置信度为0.01时极显著相关,硫化物与甲烷在置信度为0.05时不相关;COD、硫酸盐和TN浓度的变化对生活污水中甲烷的产生起关键性作用。对居民生活污水中甲烷产生规律进行温度和pH控制分析研究,实验结果表明,生活污水在25~30℃时,24 h内甲烷产生量最大值为8.6494 mg/L,明显大于其他温度段的甲烷产生量;在pH为7~8之间时,甲烷的产生量在24 h内达到的最大值为3.0477 mg/L,明显高于其他pH控制段的甲烷产生量。     

吹脱法预处理皮革废水的实验研究

对某皮革厂综合废水进行吹脱预处理实验,综合考察了影响氨氮去除的各个因素(pH值、汽液比、吹脱温度、氨氮初始浓度),同时对该预处理工艺去除铬、SS(悬浮固体浓度)、COD和硫化物的条件进行了优化,并进行了能耗及运行成本估算。结果表明:该厂皮革废水的最佳吹脱工况为pH=11,气液比=1 800,温度25~35℃,在此条件下,当进水ρ(NH3-N)=304.7 mg/L、ρ(Cr)=65.0 mg/L、ρ(SS)=1 700 mg/L、ρ(COD)=2 700 mg/L、ρ(S2-)=112.3 mg/L时,相应的去除率可达78.1%~83.5%、96.4%、88.2%、45.6%和85.0%,且吹脱法对氨氮具有较高的抗冲击负荷能力,吨水处理成本约为3.61元,可作为皮革废水的预处理工艺。