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.     

Aerobic and anaerobic transformations of sulfide in a sewer system--field study and model simulations.

The formation and fate of sulfide in a force main and a downstream-located gravity sewer were investigated in an extensive field study. Sulfide formation in the force main was significant. However, during 14 minutes of transport in the gravity sewer, the sulfide concentration decreased 30%, on average. An application of a conceptual sewer process model for simulating the formation and fate of sulfide was demonstrated. Overall, the model predicted that approximately 90% of the decrease of the sulfide concentration in the gravity sewer was the result of sulfide oxidation and that only a small fraction entered the sewer atmosphere, causing odor and corrosion. Even so, the model predicted concrete corrosion rates of up to 1.2 mm/y in the gravity sewer section.     

Modeling the reaction kinetics of Fenton's process on the removal of atrazine

The degradation of pesticide, atrazine (ATZ), 2-chloro-4-(ethylamino)-6-(isopropylamino)-s-triazine, by Fenton's reagent (FR) was investigated as a function of reagents' concentrations and ratios in a batch reactor. The degradation of ATZ was effectively achieved by hydroxyl radicals, which were generated in the FR process. The decay rates of ATZ and the oxidation capacities of FR were found to depend on the concentrations of hydrogen peroxide and ferrous ion. The removal kinetics of ATZ are initiated by a rapid decay and then followed by a much slower one. After an extended reaction time (5-10 min), the reactions ceased because the Fe(II) and H(2)O(2) were consumed and would be deactivated in the process. A mathematical model was successfully developed to describe the two-stage reaction kinetics by using two simple but critical parameters: the initial ATZ decay rate and the final oxidation capacity of Fenton's process. In general, higher [Fe(II)] or H(2)O(2) concentrations result in faster initial decay rate and higher oxidation capacity. However, the oxidation capacity is more sensitive to the initial [Fe(II)] due to the presence of side reactions as discussed in the paper.     

铁碳微电解-Fenton法预处理苯胺基乙腈生产废水的动力学研究

通过采用铁碳微电解-Fenton法预处理苯胺基乙腈生产废水的实验研究,分析了处理过程的COD降解动力学;同时研究了单纯活性炭吸附和微电解过程中COD去除率的变化。结果表明,铁碳微电解的初期COD降解过程近似符合一级反应动力学,并且得到微电解与活性炭吸附对铁碳微电解降解COD的关系式;Fenton反应中通过研究有机物浓度和过氧化氢初始浓度与反应进程的关系,建立了反应动力学模型;单纯吸附实验COD去除率在24h内快速下降,而微电解在相应时间内COD去除率波动较小,为实际应用提供了数据经验和理论依据。     

铁碳微电解-Fenton法预处理苯胺基乙腈生产废水的动力学研究

通过采用铁碳微电解-Fenton法预处理苯胺基乙腈生产废水的实验研究,分析了处理过程的COD降解动力学;同时研究了单纯活性炭吸附和微电解过程中COD去除率的变化。结果表明,铁碳微电解的初期COD降解过程近似符合一级反应动力学,并且得到微电解与活性炭吸附对铁碳微电解降解COD的关系式;Fenton反应中通过研究有机物浓度和过氧化氢初始浓度与反应进程的关系,建立了反应动力学模型;单纯吸附实验COD去除率在24 h内快速下降,而微电解在相应时间内COD去除率波动较小,为实际应用提供了数据经验和理论依据。     

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。     

Adsorption-oxidation of hydrogen sulfide on activated carbon fibers: effect of the composition and the relative humidity of the gas phase

The removal of hydrogen sulfide by oxidation-adsorption on two type carbon fibers, Actitex FC1201 and RS1301, was studied. Two kinetic steps where identified. During the first step, the degradation appears to be limited by the oxidation reaction. In the second kinetic step, the by-products inhibit the hydrogen sulfide degradation. This leads to a limitation in the carbon site's accessibility and to a lower kinetic. The Langmuir-Hinshelwood model was used to correlate the experimental results and to estimate the kinetic (k) and the Langmuir adsorption (K) constants. For FC1201 fibers, the kinetic constant (k) is five time higher and the adsorption constant is five time lower compared to the RS1301 fibers. The role of the humidity was found to be highly beneficial for the removal of hydrogen sulfide. Especially in the second kinetic step, where it removes the by-product formed and therefore delays the occurrence of this low kinetic step. The kinetic constant (k) is strongly influenced by humidity while the Langmuir adsorption constant (K) seems independent. The effect of the nature of the gas phase on the reaction kinetic was also studied. Under a dry atmosphere, we note that the oxidation-reaction occurs even if the gaseous oxygen is not present. This oxidation is due to the oxygen surface function of the carbon fibers. Moreover, the degradation kinetic is faster under a dry nitrogen atmosphere. The presence of water traces leads to the acidification of the carbon surface, under oxygen or carbon dioxide atmospheres, and hence limits the hydrogen sulfide dissociation. In a humid atmosphere, the oxygen or carbon dioxide leads to a faster reaction kinetic. The acidification of the carbon surface is largely counterbalanced by the dissolution of the by-products.     

Hg reactions in the presence of chlorine species: homogeneous gas phase and heterogeneous gas-solid phase

The kinetics of Hg chlorination (with HCl) was studied using a flow reactor system with an online Hg analyzer, and speciation sampling using a set of impingers. Kinetic parameters, such as reaction order (alpha), overall rate constant (k'), and activation energy (Ea), were estimated based on the simple overall reaction pathway. The reaction order with respect to C(Hg), k', and Ea were found to be 1.55, 5.07 x 10(-2) exp(-1939.68/T) [(microg/m3)(-055)(s)(-1)]. and 16.13 [kJ/ mol], respectively. The effect of chlorine species (HCl, CH2Cl2) on the in situ Hg capture method previously developed (28) was also investigated. The efficiency of capture of Hg by this in situ method was higher than 98% in the presence of chlorine species. Furthermore, under certain conditions, the presence of chlorine enhanced the removal of elemental Hg by additional gas-phase oxidation.     

淀粉微球对苯酚的吸附性能研究

以可溶性淀粉为原料,N,N’-亚甲基双丙烯酰胺(MBAA)为交联剂,通过反相悬浮聚合得到淀粉微球作为吸附载体,研究了pH、吸附时间、温度对其苯酚吸附性能的影响,以及淀粉微球吸附苯酚的热力学和动力学特性,并利用扫描电镜仪、红外光谱仪对淀粉微球的结构进行了表征。结果表明,淀粉微球粒度分布均匀,表面粗糙多孔,具有相当大的孔容积和比表面积,具有较好的吸附性能;在20℃、pH为5.3时,吸附30 min后,淀粉微球对苯酚的吸附容量达到饱和,最大吸附量为18.71 mg/g;采用准二级吸附动力学方程能更好地描述淀粉微球对苯酚的吸附行为,淀粉微球对苯酚的吸附是以化学吸附为主控步骤的作用过程,淀粉微球对苯酚的吸附主要是通过氢键作用来完成的。     

Kinetics of simazine advanced oxidation in water

Comparison of the effects and kinetics of UV photolysis and four advanced oxidation systems (ozone, ozone/hydrogen peroxide, ozone/UV radiation and UV radiation/hydrogen peroxide) for the removal of simazine from water has been investigated. At the conditions applied, the order of reactivity was ozone < ozone/hydrogen peroxide < UV radiation < ozone/UV radiation and UV radiation/hydrogen peroxide. Rate constants of the reactions between ozone and simazine and hydroxyl radical and simazine were found to be 8.7 M-1s-1 and 2.1 x 10(9) M-1s-1, respectively. Also, a quantum yield of 0.06 mol.photon-1 was found for simazine at 254 nm UV radiation. The high value of the quantum yield corroborated the importance of the direct photolysis process. Percentage contributions of direct reaction with ozone, reaction with hydroxyl radicals and direct photolysis were also quantified.     

Photocatalytic oxidation of methyl orange in a three-phase fluidized bed reactor

The photocatalytic oxidation of methyl orange under weak illumination conditions was carried out in two different types of fluidized bed reactors. TiO2 powder was employed as the photocatalysts and a 15 W low pressure mercury lamp was used as the light source and the reactor volume was 2.5 l. The parametric study of photocatalytic oxidation of methyl orange in two different types of fluidized beds was investigated; effect of catalyst loadings, pH, air flow rate, initial concentration and oxygen concentration on the oxidation reaction rate. The experimental results were analyzed in conjunction with the characteristics of fluidized bed and the reactor geometry effect on the reaction rate was analyzed.     

Ozonation of aqueous solution of alpha endosulfan

Ozonation of alpha endosulfan and the effects of some parameters such as pH, temperature and partial pressure on ozonation were investigated and the kinetic constants were calculated in this study. Alpha endosulfan solutions were ozonated in a lab-scale semi-batch reactor under variable experimental conditions. Increase in dissolved ozone concentration had a positive effect on oxidation rate. Alpha endosulfan could be removed up to 94% at pH 4 for an ozonation time of 60 minutes. The oxidation reaction was found to be of second order and of first order with respect to both ozone and alpha endosulfan. The temperature dependent reaction expression of alpha endosulfan was obtained as kd = (1.889 exp(- 2.21 x 10(-3)/T). It was concluded that, although the rate of reaction was lower than the rate of other pesticide oxidation reported in the literature. alpha endosulfan presented an obvious reaction to ozonation.     

Photocatalytic production of hydrogen in single component and mixture systems of electron donors and monitoring adsorption of donors by in situ infrared spectroscopy

The photocatalytic production of hydrogen using aqueous Pt/TiO2 suspension has been investigated in single component and mixture systems of electron donors (pollutants). The reaction systems consisted of oxalic acid, formic acid and formaldehyde, respectively. The adsorption of these donors on TiO2 was also monitored by in situ attenuated total reflection infrared spectroscopy (ATRIR). In the single component systems, the efficiency order of electron donors is as follows: H2C2O4 > HCOOH > HCHO. The order is consistent with the order of adsorption affinity of the electron donors on TiO2 determined by ATRIR, which suggests a link between the strength of surface interaction and the efficiency of photocatalytic hydrogen evolution. In the binary mixture systems, competitive inhibition kinetics is observed. When a donor adsorbed strongly on TiO2 in a state of saturated adsorption in a binary system, the overall rate of the hydrogen evolution is consistent with that of decomposition of the donor, and the system can be treated as a single component system.     

Treatment of dilute methylene blue-containing wastewater by coupling sawdust adsorption and electrochemical regeneration

In the present work, the coupling of adsorption and electrochemical oxidation on a boron-doped diamond (BDD) electrode to treat solutions containing dyes is studied. This coupling may be convenient for the treatment of diluted pollutant that is limited by the low rate of electrooxidation due to mass-transfer limitation. A pre-concentration step by adsorption could minimize the design of the electrochemical reactor. The adsorbent chosen was mixed with softwood sawdust, and methylene blue was chosen as the model dye molecule. Isotherms of adsorption and kinetics were investigated as well as the effects of current density and regeneration time. The BDD electrochemical oxidation of methylene blue adsorbed onto sawdust led simultaneously to its degradation and sawdust regeneration for the next adsorption. It was observed that multiple adsorption and electrochemical regeneration cycles led to an enhancement of adsorption capacity of the sawdust. This study demonstrated that adsorption–electrochemical degradation coupling offers a promising approach for the efficient elimination of organic dyes from wastewater.     

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)。     

Adsorption of hydrogen sulfide on montmorillonites modified with iron

Sodium-rich montmorillonite was modified with iron in order to introduce active centers for hydrogen sulfide adsorption. In the first modification, interlayer sodium cations were exchanged with iron. In another modification, iron oxocations were introduced to the clay surface. The most elaborated modification was based on doping of iron within the interlayer space of aluminum-pillared clay. The modified clay samples were tested as hydrogen sulfide adsorbents. Iron-doped samples showed a significant improvement in the capacity for H2S removal, despite of a noticeable decrease in microporosity compared to the initial pillared clay. The smallest capacity was obtained for the clay modified with iron oxocations. Variations in adsorption capacity are likely due to differences in the chemistry of iron species, degree of their dispersion on the surface, and accessibility of small pores for H2S molecule. The results suggest that on the surface of iron-modified clay hydrogen sulfide reacts with Fe(+3) forming sulfides or it is catalytically oxidized to SO2 on iron (hydro)oxides. Subsequent oxidation may lead to sulfate formation.     

Biofiltration Control of Hydrogen Sulfide 2. Kinetics,Biofilter Performance,and Maintenance

The kinetics of H₂S oxidation in a biofilter were evaluated and the reaction rates determined to be first-order at low concentrations (<200 ppm), zero-order at high concentrations (>400 ppm), and fractional-order in the intermediate concentration range for H₂S in the inlet waste gas. The overall performance of the biofilter system and changes in compost properties were investigated for 200 days of operation. The compost biofiiter showed good buffering capacities to variations in gas flow rate and pollutant (H₂S) loading impacts. Hydrogen sulfide removal efficiencies exceeding 99.9% were consistently observed. System acidification and sulfate accumulation were identified as inhibitors of required biological activity. Routine washing of the compost effectively mitigated these deficiencies. System upset was determined to be caused by compost dry-out or system overloading. Methods were developed to provide for recovery of contaminated filter material.     

The removal of hydrogen sulfide in solution by ferric and alum water treatment residuals

This work investigated the characteristics and mechanisms of hydrogen sulfide adsorption by ferric and alum water treatment residuals (FARs) in solution. The results indicated that FARs had a high hydrogen sulfide adsorption capacity. pH 7 rather than higher pH (e.g. pH 8-10) was favorable for hydrogen sulfide removal. The Yan model fitted the breakthrough curves better than the Thomas model under varied pH values and concentrations. The Brunauer-Emmett-Teller surface area and the total pore volume of the FARs decreased after the adsorption of hydrogen sulfide. In particular, the volume of pores with a radius of 3-5 nm decreased, while the volume of pores with a radius of 2 nm increased. Therefore, it was inferred that new adsorption sites were generated during the adsorption process. The pH of the FARs increased greatly after adsorption. Moreover, differential scanning calorimetry analysis indicated that elemental sulfur was present in the FARs, while the derivative thermal gravimetry curves indicated the presence of sulfuric acid and sulfurous acid. These results indicated that both oxidization and ligand exchange contribute to the removal of hydrogen sulfide by FARs. Under anaerobic conditions, the maximum amount of hydrogen sulfide released was approximately 0.026 mg g(-1), which was less than 0.19% of the total amount adsorbed by the FARs. The hydrogen sulfide that was released may be re-adsorbed by the FARs and transformed into more stable mineral forms. Therefore, FARs are an excellent adsorbent for hydrogen sulfide.     

培养方式对废水脱氮与沼气脱硫污泥驯化影响

实验研究了底物、接种污泥和微生物生长方式对猪场废水脱氮和沼气脱硫耦联污泥驯化及活性恢复的影响,以解决快速富集培养废水脱氮与沼气脱硫微生物的问题。研究发现,就脱氮脱硫均达到60%的时间而言,接种厌氧污泥反应器为9 d,比接种好氧污泥反应器(18 d)和不接种污泥加填料反应器(21 d)更短。以含氮含硫废水为底物驯化时,接种厌氧污泥更有利于脱氮脱硫污泥的驯化;而同为接种好氧污泥时,以含氮含硫废水为底物的驯化方式更有利于脱氮脱硫污泥的驯化。污泥活性恢复实验中,以含氮废水+沼气(H2S)为底物培养驯化的污泥,硫转化活性恢复所用的时间为15 d,比含氮含硫废水为底物驯化污泥的活性恢复时间更长。     

内循环管式光催化反应器降解水中喹啉的动力学研究

采用内循环管式光催化反应器,考察不同的温度、有机物底物浓度、光照强度、曝气强度等因素对水中喹啉的降解效果影响,在此基础上进行降解动力学研究。实验结果表明:温度、喹啉初始浓度、光照强度、曝气强度等因素与喹啉的催化降解呈现良好的相关关系,喹啉的表观吸附平衡常数为0.0244 L/mg,溶解氧表观吸附平衡常数为2.11,反应活化能为16.734 kJ/mol,光照强度修正指数为0.525。