Catalytic destruction of dichloromethane using perovskite-type oxide catalysts

Dichloromethane (DCM, also known as methylene chloride [CH2Cl2]) is often present in industrial waste gas and is a valuable chemical product in the chemical industry. This study addresses the oxidation of airstreams that contain CH2Cl2 by catalytic oxidation in a tubular fixed-bed reactor over perovskite-type oxide catalysts. This work also considers how the concentration of influent CH2Cl2 (Co = 500-1000 ppm), the space velocity (GHSV = 5000-48,000 1/hr), the relative humidity (RH = 10-70%) and the concentration of oxygen (O2 = 5-21%) influence the operational stability and capacity for the removal of CH2Cl2. The surface area of lanthanum (La)-cobalt (Co) composite catalyst was the greatest of the five perovskite-type catalysts prepared in various composites of La, strontium, and Co metal oxides. Approximately 99.5% CH2Cl2 reduction was achieved by the catalytic oxidation over LaCoO3-based perovskite catalyst at 600 degrees C. Furthermore, the effect of the initial concentration and reaction temperature on the removal of CH2Cl2 in the gaseous phase was also monitored. This study also provides information that a higher humidity corresponds to a lower conversion. Carbon dioxide and hydrogen chloride were the two main products of the oxidation process at a relative humidity of 70%.     

氯胺消毒对三卤甲烷类消毒副产物的控制研究

在氯消毒研究的基础上,研究氯胺对消毒副产物的控制,将氯与氨氮的比值降至5,能够使单独氯消毒所生成消毒副产物减少89%,二溴一氯甲烷也不再检出;消毒副产物的生成量与氯胺的投加量呈很好的线性关系;接触时间对消毒副产物的生成量影响很小,24 h增加缓慢;pH升高至8消毒副产物的总量比pH为7时减少82.3%,一溴二氯甲烷不再检出;氯胺代替氯消毒能够很好地控制溴代消毒副产物种类和总量.     

氯胺消毒对三卤甲烷类消毒副产物的控制研究

在氯消毒研究的基础上,研究氯胺对消毒副产物的控制,将氯与氨氮的比值降至5,能够使单独氯消毒所生成消毒副产物减少89%,二溴一氯甲烷也不再检出;消毒副产物的生成量与氯胺的投加量呈很好的线性关系;接触时间对消毒副产物的生成量影响很小,24 h增加缓慢;pH升高至8消毒副产物的总量比pH为7时减少82.3%,一溴二氯甲烷不再检出;氯胺代替氯消毒能够很好地控制溴代消毒副产物种类和总量.     

Effects of chlorination on the adhesion strength and deflocculation of activated sludge flocs.

A side effect of the application of chlorine for controlling filamentous bulking is deflocculation of floc-forming bacteria, which may cause unacceptable effluent deterioration depending on dosing. It was assumed that chlorine may adversely affect the adhesion ability of floc bacteria, promoting their erosion in shear flow. The effect of chlorination on the strength of activated sludge flocs was investigated. The adhesion-erosion (AE) model developed by Mikkelsen and Keiding was used to interpret results from deflocculation tests with varying shear and solids concentration. The AE model yields the adhesion enthalpy (deltaHG/R) of cells in sludge flocs and parameters from the model were used to quantify the sludge in terms of floc strength. Two activated sludges with different initial characteristics were studied. The resulting model parameters showed that the AE model was suitable for quantifying the bond energy of particles to the activated sludge exposed to chlorine. For one activated sludge, adhesion of cells was largely unaffected by the applied chlorine doses. A second sludge showed reduced adhesion strength with chlorine, leading to increasing deflocculation. The simple batch test and AE model proved valuable for assessing the effect of chlorination on the flocs in activated sludge. By use of these procedures, it is possible to determine acceptable chlorine dosing to avoid excessive deflocculation and effluent deterioration.     

Precursors and nitrogen origins of trichloronitromethane and dichloroacetonitrile during chlorination/chloramination

The formation of trichloronitromethane (TCNM) and dichloroacetonitrile (DCAN) was investigated during chlorination and chloramination of 31 organic nitrogen (org-N) compounds, including amino acids, amines, dipeptides, purines, pyrimidones and pyrroles. Tryptophan and alanine generated the greatest amount of TCNM during chlorination process and asparagine and tyrosine yielded the highest amount of TCNM during chloramination process. Tryptophan, tyrosine, asparagine, and alanine produced more DCAN than other org-N compounds regardless of chlorination or chloramination. TCNM and DCAN formation was higher by chlorination than by chloramination. NH₂Cl:org-N molar ratios, reaction time, and pH affected N-DBPs formation in varying degrees. TCNM and DCAN yields were usually high during chloramination of tyrosine, asparagine, and methylpyrrole under the following reaction conditions: NH₂Cl:org-N molar ratios greater than 10, reaction time for 1 d, and at pH 7.2. NH₂Cl as a major nitrogen origin in TCNM and DCAN was confirmed via labeled ¹⁵N-monochloramine during chloramination of tyrosine, asparagine and methylpyrrole. In contrast, the majority of nitrogen in TCNM originated from glycine, and that in DCAN originated from pyrrole. Based on the intermediates identified by gas chromatography/mass spectrometry (GC/MS), a pathway scheme was proposed for TCNM and DCAN formation.     

活性炭纤维电极对TAIC的电催化氧化

以活性炭纤维为阳极,不锈钢电极为阴极,研究了活性炭纤维电极电催化氧化去除水中三烯丙基异氰脲酸酯(TAIC)的方法.采用单因素实验法研究pH,电流密度,电解质种类和浓度对电催化氧化性能的影响,并找到最佳反应条件.实验结果表明,在TAIC模拟废水中,TAIC初始浓度为150 mg/L,pH为7,电流密度为50 mA/cm2,以0.06 mol/L Na2SO4为电解质溶液时反应效果最佳,60 min时TAIC的去除率为90.7%.     

Catalytic oxidation of TNT by activated carbon

Activated carbon can remove 2,4,6-trinitrotoluene (TNT) and 1,3,5-trinitrobenzene (TNB) from aqueous solution and promote oxidation of TNT. After equilibrating a 0.35 mM TNT solution with activated carbon (0.2-1% w/v), HPLC and GC/MS analysis confirmed the presence of 2,4,6-trinitrobenzaldehyde (TNBAld) and 2,4,6-trinitrobenzene (TNB), and provided strong evidence supporting 2,4,6-trinitrobenzyl alcohol (TNBAlc) as an intermediate of TNT oxidation. After 6 d, TNT and its oxidation products were strongly bound to the activated carbon, while TNB was extractable with acetonitrile. Observations indicate that activated carbon catalyzes TNT oxidation to TNBAlc, which is readily oxidized to TNBAld and TNB in the absence of activated carbon under dark conditions. While adsorbed TNB was extractable with acetonitrile, activated carbon promoted rapid TNT oxidation and formation of unextractable residues. Strong binding is attributed to catalyzed oxidation of the TNT methyl group, probably through a free radical mechanism, and subsequent chemisorption of oligomers and polymerized products that are not desorbed from micropores. Our observations indicate TNT oxidation and bound residue formation after sorption by activated carbon increases the effectiveness of activated carbon to decontaminate water.     

Maximum nitrogen removal in the step-feed activated sludge process.

This paper presents a mathematical framework that can be used to determine the flow distributions for a step-feed activated sludge process that result in maximum nitrogen removal. The model indicates that nitrogen removal efficiency in a step-feed activated sludge process is highly dependent on the ultimate biochemical oxygen demand (BOD(L))-to-total Kjeldahl nitrogen (TKN) ratio of the wastewater. For typical domestic wastewater, which has a relatively high BOD(L)-to-TKN ratio, the step-feed process will outperform the Modified Ludzack-Ettinger process for nitrogen removal, when the flow to each step is optimally distributed. Using plant-specific water quality data and operating conditions from a 1-year period, nitrogen removal performance for four step-feed activated sludge plants operated by the Sanitation Districts of Los Angeles County (California) was calculated using the developed model. The calculated nitrogen removal efficiencies match well with the actual plant performance data. These results validate the model as a useful tool for predicting nitrogen removal in a step-feed activated sludge process. Other analyses revealed that improvements in nitrogen removal at existing facilities are achievable by adjusting the split of primary effluent flow to each anoxic zone several times during the day. The timing of the adjustments and the optimal flow splits can be determined from data on diurnal fluctuations in BOD(L) and TKN concentrations. An example is provided to illustrate the application of such an operating strategy and the potential enhancement of nitrogen removal.     

Kinetic and adsorption study of acid dye removal using activated carbon

The adsorption of three acid dyes, Acid Red 97, Acid Orange 61 and Acid Brown 425 onto activated carbon was studied for the removal of acid dyes from aqueous solutions at room temperature (25 degrees C). The adsorption of each dye with respect to contact time was then measured to provide information about the adsorption characteristics of activated carbon. The rates of adsorption were found to conform to the pseudo-second-order kinetics with a good correlation. The experimental isotherms obtained, except for Acid Orange 61 studied in mixture, were of the S-type in terms of the classification of Giles and co-workers. The best fit of the adsorption isotherm data was obtained using the Freundlich model. When a comparative study was made of the results obtained with single and mixed dyes, it can be seen that some of them affect others and modify their behavior in the adsorption process. The results indicate that activated carbon could be employed for the removal of dyes from wastewater.     

Breakpoint chlorination curves of greywater.

A study on chlorination of raw greywater with hypochlorite is reported in this paper. Samples were chlorinated in a variety of conditions, and residual chlorine (Cl2) was measured spectrophotometrically. For each sample, the chlorination curve (chlorine residuals versus chlorine dose) was obtained. Curves showed the typical hump-and-dip profile attributable to the formation and destruction of chloramines. It was observed that, after reactions with strong reductants and chloramines-forming compounds, the remaining organic matter exerted a certain demand of chlorine. The evolution of chlorination curves with addition of ammonia and dodecylbencene sulfonate sodium salt and with dilution of the greywater sample were studied. In addition, chlorination curves at several contact times have been obtained, resulting in slower chlorine decay in the hump zone than in the dip zone. In addition, the decay of coliforms in chlorinated samples was also investigated. It was found that, for a chlorination dosage corresponding to the maximum of the hump zone (average 8.9 mg Cl2/ L), samples were negative in coliforms after 10 to 30 minutes of contact time. After-growth was not observed within 3 days after chlorination. Implications in chlorination treatments of raw greywater can be derived from these results.     

餐厨垃圾与剩余污泥协同发酵提升低C/N污水脱氮效能的中试研究

我国城镇污水处理厂进水碳源普遍偏低,严重影响生物脱氮效能。外加碳源会造成大量化学品消耗及碳排放,与双碳战略背道而驰。考察了餐厨垃圾和剩余污泥联合发酵中试装备 (规模10 t·d⁻¹) 制备挥发性脂肪酸 (VFA) 效能,并将生产的VFA发酵液投加至昆山市某城镇污水处理厂,以减少外源乙酸钠碳源投加量,以期探索城市污水与有机固废的协同、高效、低碳处理技术。结果表明：餐厨垃圾与剩余污泥体积比为7∶3时,VFA质量浓度最高,达到54.3 g·L⁻¹ (以COD计) ,乙酸和丙酸质量分数分别为36.5%和22.8%;在批次发酵中试实验中,VFA最高质量浓度达67.5 g·L⁻¹ (以COD计) ,最低质量浓度为42.4 g·L⁻¹ (以COD计) ,平均质量浓度为55.0 g·L⁻¹ (以COD计) ;对比3类碳源的反硝化实验结果,投加乙酸钠组1.5 h脱氮率为86.5%,投加发酵液组4.5 h脱氮率为81.0%,投加餐厨垃圾组仅为69.8%;根据出水总氮预警阈值 (>8 mg·L⁻¹) 补加发酵液,替代部分乙酸钠,通过实际污水厂运行数据,拟合得到发酵液投量X (m³) 与乙酸钠吨水节约量Y (g·m⁻³) 的线性关系式Y=4.9X+3.5,其中R²=0.91。该研究结果可为联合发酵制备优质碳源提升污水厂脱氮工程应用提供参考。     

Feed-forward dose control of wastewater chlorination using on-line pH and ORP titration

In this study, a simple automatic pH-ORP titration device was developed for identifying the various ammonia concentrations and chlorine dose requirements for wastewater chlorination by identifying the peaks in the ORP-slope profiles and knees/valleys in the pH profiles. In addition, breakpoint chlorination experiments have shown that the ORP values at the monochloramine humps and breakpoints are linearly correlated with the ammonia concentrations. Therefore, a feed-forward control strategy, based on the chlorine/ammonia weight ratio (Cl/N), is proposed in this paper, to control the chlorine doses for a continuous wastewater chlorination experiment in a laboratory-scale reactor. The result of this continuous wastewater chlorination experiment has shown that the pH-ORP titration was able to precisely determine the variations of ammonia concentrations in the chlorination influent. Under this control strategy, effective and stable disinfection efficiencies in terms of total coliform count were obtained.     

Investigation of OUR and NUR experiments for nitrogen and phosphorus removal with activated sludge: a lab-scale study

Activated sludge systems are widely used in wastewater treatment. Organic carbon removal and nutrient removal are important for stringent water discharge standards. Therefore, activated sludge systems are widely used to remove carbon, nitrogen and phosphorus in new wastewater treatment systems or upgrades of existing systems. The determination of system compounds and kinetic parameters for modelling of these systems are important. For this purpose, respirometric measurements are used to reveal the electron consumption rate of biomass. In order to determine OUR (oxygen uptake rate) and NUR (nitrate uptake rate) parameters, a laboratory scale activated sludge system, including anaerobic, anoxic and aerobic zones, was developed. The performance of the system was continuously controlled from influent and effluent samples. OUR and NUR measurements indicated the kind of nitrogen-phosphorus removal systems required. Moreover, phosphorus uptake in the anoxic zone was investigated. It was found that phosphorus uptake in the anaerobic zone was related to substrate type consumed biologically. The OUR and NUR were found to be lower than in continuous activated sludge measurements. This may be because the mixed culture of the system affected the system performance, owing to competition between denitrification bacteria and poly-P bacteria.     

Peracetic acid disinfection: a feasible alternative to wastewater chlorination.

The paper summarizes the results of a bench-scale study to evaluate the feasibility of using peracetic acid (PAA) as a substitute for sodium hypochlorite both for discharge into surface water and for agricultural reuse. Trials were carried out with increasing doses (1, 2, 3, 5, 10, and 15 mg/L) and contact times (6, 12, 18, 36, 42, and 54 minutes) to study disinfectant decay and bacterial removal and regrowth, using fecal coliform and Escherichia coli (E. coli) as process efficiency indicators. Peracetic acid decay kinetics was evaluated in tap water and wastewater; in both cases, PAA decays according to first-order kinetics with respect to time, and a correlation was found between PAA oxidative initial consumption and wastewater characteristics. The PAA disinfection efficiency was correlated with operating parameters (active concentration and contact time), testing different kinetic models. Two data groups displaying a different behavior on the basis of initial active concentration ranges (1 to 2 mg/L and 5 to 15 mg/L, respectively) can be outlined. Both groups had a "tailing-off" inactivation curve with respect to time, but the second one showed a greater inactivation rate. Moreover, the effect of contact time was greater at the lower doses. Hom's model, used separately for the two data groups, was found to best fit experimental data, and the disinfectant active concentration appears to be the main factor affecting log-survival ratios. Moreover, the S-model better explains the initial resistance of E. coli, especially at low active concentrations (< 2 mg/L) and short contact times (< 12 minutes). Microbial counts, performed by both traditional methods and flow cytometry, immediately and 5 hours after sample collection (both with or without residual PAA inactivation), showed that no appreciable regrowth took place after 5 hours, neither for coliform group bacteria, nor for total heterotrophic bacteria.     

Catalytic hydrothermal treatment of pulping effluent using a mixture of Cu and Mn metals supported on activated carbon as catalyst

The present study was performed to investigate the performance of activated carbon-supported copper and manganese base catalyst for catalytic wet oxidation (CWO) of pulping effluent. CWO reaction was performed in a high pressure reactor (capacity?=?0.7 l) at temperatures ranging from 120 to 190 °C and oxygen partial pressures of 0.5 to 0.9 MPa with the catalyst concentration of 3 g/l for 3 h duration. With Cu/Mn/AC catalyst at 190 °C temperature and 0.9 MPa oxygen partial pressures, the maximum chemical oxygen demand (COD), total organic carbon (TOC), lignin, and color removals of 73, 71, 86, and 85 %, respectively, were achieved compared to only 52, 51, 53, and 54 % removals during the non-catalytic process. Biodegradability (in terms of 5-day biochemical oxygen demand (BOD₅) to COD ratio) of the pulping effluent was improved to 0.38 from an initial value of 0.16 after the catalytic reaction. The adsorbed carbonaceous fraction on the used catalyst was also determined which contributed meager TOC reduction of 3–4 %. The leaching test showed dissolution of the metals (i.e., Cu and Mn) from the catalysts in the wastewater during CWO reaction at 190 °C temperature and 0.9 MPa oxygen partial pressures. In the future, the investigations should focus on the catalyst reusability.     

Immobilized cell augmented activated sludge process for enhanced nitrogen removal from wastewater.

The immobilized cell augmented activated sludge (ICAAS) system combines a cell immobilization technique and an offline enricher-reactor for the bioaugmentation of the activated sludge system to improve treatment performances. In this study, enhanced nitrogen removal using ICAAS was investigated. Laboratory-scale, offline, batch enricher-reactors were used to maintain nitrification and denitrification activities of coimmobilized nitrifiers and denitrifiers used to augment a laboratory-scale completely mixed activated sludge system (CMAS) treating synthetic wastewater. Cellulose triacetate was the media used to entrap nitrifiers and denitrifiers at a 2:1 mass ratio. The ICAAS augmented with the coimmobilized cells between 5 and 20% by volume gained 24 +/- 5% higher nitrogen removal than a control CMAS, which provided nitrogen removal of 28 +/- 7%. The ICAAS scheme is a viable alternative for upgrading existing activated sludge systems to gain better nitrogen removal. .     

Effect of influent nitrogen speciation on organic nitrogen occurrence in activated sludge process effluents

The effect of influent nitrogen composition on organic nitrogen production in a sequencing batch reactor (SBR) activated sludge process was investigated. A laboratory-scale SBR was fed with three different type synthetic wastewaters with varying nitrogen compositions (phase I = nitriloacetic acid + ammonium [NH4-N], phase II = NH(4-)N, and phase III = amino acid mixture + NH(4-)N) was operated. The effluent contained approximately 1 to 2 mg N/L organic nitrogen, even though there was no organic nitrogen in influent. The effluent organic nitrogen increased to approximately 4 mg N/L when the influent composition was changed and then stabilized at <2 mg N/L. The maximum nitrifier growth rate constants (microN) were calculated as 0.91+/-0.10 to 1.14+/-0.08 day-1, 0.82 +/-0.13 day-1, and 0.89+/-0.08 day-1 at 20 degrees C for the three different influent compositions. The effluent colloidal organic nitrogen (CON) was negligible, suggesting that the effluent CON found in full-scale plants may be the result of influent-derived suspended matter.     

Experimental study on the removal of PAHs using in-duct activated carbon injection

This paper presents the incineration tests of municipal solid waste (MSW) in a fluidized bed and the adsorption of activated carbon (AC) on polycyclic aromatic hydrocarbons (PAHs). An extraction and high performance liquid chromatography (HPLC) technique was used to analyze the concentrations of the 16 US EPA specified PAHs contained in raw MSW, flue gas, fly ash, and bottom ash. The aim of this work was to decide the influence of AC on the distribution of PAHs during the incineration of MSW. Experimental researches show that there were a few PAHs in MSW and bottom ash. With the increase of AC feeding rate, the concentrations of three- to six-ring PAHs in fly ash increased, and the concentration of two-ring PAH decreased. The total-PAHs in flue gas were dominated by three-, and four-ring PAHs, but a few two-, five-ring PAHs and no six-ring PAHs were found. PAHs could be removed effectively from flue gas by using in-duct AC injection and the removal efficiencies of PAHs were about 76-91%. In addition, the total toxic equivalent (TEQ) concentrations of PAH in raw MSW, bottom ash, fly ash, and flue gas were 1.24 mg TEQ kg-1, 0.25 mg TEQ kg-1, 6.89-9.67 mg TEQ kg-1, and 0.36-1.50 microg TEQ Nm-3, respectively.