Reactive Dye Removal Using Inorganic–Organic Composite Material: Kinetics,Mechanism, and Optimization

An inorganic–organic composite material (MCPAM) consisting of magnesium chloride and polyacrylamide, was applied to remove reactive dye (Cibacron Red FN-R) from aqueous solution through coagulation–flocculation process. MCPAM with the ratio of 90% MgCl₂/10% PAM was the best ratio in removing reactive dye. Kinetics of reactive dye removal was investigated using pseudo-kinetics model and it fits pseudo-second-order reaction model. The mechanism of reactive dye removal was investigated through physicochemical properties of supernatant, flocs, and sludge. The change of conductivity and pH denotes the interactions between reactive dye and MCPAM. The chemical structure, settling, and microstructure of sludge indicate the formation of sludge during coagulation–flocculation process. The settled sludge volume and sludge volume index (SVI) that of MCPAM was lower than that of MgCl₂. The flocs formed using MCPAM was also relatively compact and larger in size compared to that of MgCl₂. The reactive dye removal was optimized through central composite design whereby color removal (%) and chemical oxygen demand (COD) reduction (%) were optimized by five operating factors, namely, concentration of dye, pH, dosage of MCPAM, agitation speed, and agitation time. The optimal values reported for color removal (%) and COD reduction (%) were of 97–98% and 60–81%, respectively.     

磷钨酸均相光催化还原降解水中偶氮染料酸性大红3R

以磷钨酸(H3PW12O4记为PW12)作为光催化剂,在异丙醇作为电子给体的条件下对偶氮染料酸性大红3R（记为AR3R）进行光催化均相还原脱色研究。循环伏安法、暗反应、O2竞争抑制等实验表明杂多蓝（PW12O404-）对AR3R 具有明显的还原脱色作用。实验研究了催化剂PW12用量、异丙醇浓度、染料浓度、盐浓度对PW12/异丙醇光催化还原降解酸性大红3R的影响。结果表明：AR3R的光催化脱色速率随催化剂PW12、异丙醇浓度的增加而增加,最后趋于恒定;随染料初始浓度增加,初始光解速率增大,且符合Langmuir-Hinshelwood动力学方程;随盐浓度增加,染料脱色速率减小,表现为负的盐效应。由此推测AR3R与光反应生成的杂多蓝预先进行复合,然后发生电子转移引起偶氮染料还原脱色,杂多蓝氧化复原。本研究结果表明磷钨酸/异丙醇/UV绿色光催化还原体系能够有效用于偶氮染料废水的还原脱色处理。     

Feasibility of 2,4,6-Trichlorophenol and Malonic Acid as Metabolic Uncoupler for Sludge Reduction in the Sequence Batch Reactor for Treating Organic Wastewater

The activated sludge process generates a large amount of excess sludge as a byproduct, which is one of the most serious challenges in biological wastewater treatment. In the present study, the feasibility of 2,4,6-trichlorophenol (TCP) and malonic acid (MA) as metabolic uncouplers to reduce sludge generation in the sequence batch reactor (SBR) for treating organic wastewater for a long period was studied. The results showed that 2 mg/L TCP could reduce sludge generation by about 47%, while chemical oxygen demand (COD) removal efficiency and sludge settlability were not obviously influenced. Although 10 mg/L MA could also reduce excess sludge production by about 30% while slightly affecting COD removal, it seriously deteriorated sludge settlability. Accordingly, TCP is a better uncoupler for sludge reduction for a longer period in the SBR for treating organic wastewater, and MA can only be used as a short-term or transitional uncoupler. Microscopic and 16S ribosomal deoxyribonucleic acid analyses showed that the microbial population of sludge varied when uncouplers were fed to the activated sludge system. Occurrence of large amounts of filament and the disappearance of protozoa may be the main reason for the aggravation of sludge settlability under uncoupled metabolic conditions caused by MA.     

Optimization of multiple parameters for treatment of coking wastewater using Fenton oxidation

Present study deals with the treatment of coking wastewater (CWW) using Fenton oxidation process for the degradation of pollutants containing chemical oxygen demand (COD), phenol and cyanide. The experiments were performed in batch mode to study the effect of operating parameters like initial pH (pH_i), temperature (T), oxidant H₂O₂ amount, catalyst mass loading (Cw) and treatment time (t_R). The response surface methodology (RSM) gave optimum value of pH, H₂O₂, Cw and t_R as 3, 0.3 M, 1.85 g/L (0.0266 M) and 1.52 h. At this optimum operating condition maximum 84.66% COD, 88.46% phenol and 79.34% cyanide reduction were achieved from initial value of COD (COD_i) = 2810.0 mg/L, phenol_i = 283.0 mg/L and cyanide_i = 18.88 mg/L. Results reflect that Fenton oxidation is an effective process for the reduction of pollutants present in CWW. The CWW treated by Fenton oxidation having average value COD = 590.0 mg/L, phenol = 39.49 mg/L and cyanide = 5.2 mg/L was further treated by adsorption process as second stage treatment, and these values were reached to COD = 199.0 mg/L, phenol = 0.0 mg/L and cyanide = 2.36 mg/L. The response surface methodology (RSM) was used for the designing and optimization of the experiments. Analysis of variance (ANOVA) suggested the high regression coefficient R² = 0.999 and 0.993 for COD and phenol removal respectively. The two stage treated CWW can be recycled and reused in same industry for various purpose.     

化学需氧量在线自动监测仪示值误差的检定

介绍化学需氧量(COD)在线自动监测仪示值误差的检定方法及注意事项。选取基准试剂邻苯二甲酸氢钾,依次配制零点溶液和质量浓度分别为50,150,500 mg/L的COD标准物质溶液,用于检定COD maxⅡ型在线监测仪的示值误差。直接配制溶液为100 mg/L的COD标准溶液,与相同浓度的标准物质溶液GBW(E)082219进行比较,结果符合检定规程JJG 1012–2006的要求。检定结果表明:以重铬酸钾为氧化剂时,邻苯二甲酸氢钾的COD氧化值呈线性关系,可直接配制100 mg/L的COD标准溶液;检定COD maxⅡ型在线监测仪,每次需要的标准溶液体积为100 m L,综合考虑,进行示值误差检定时,每种浓度至少配制500 m L。作为还原性标准物质用于检定仪器示值误差,邻苯二甲酸氢钾可能无法准确反映水体中有机物的真实还原情况,具有一定的局限性。     

Feasibility of treating swine manure in an anaerobic sequencing batch biofilm reactor with mechanical stirring

Anaerobic sequencing batch reactors containing granular or flocculent biomass have been employed successfully in the treatment of piggery wastewater. However, the studies in which these reactors were employed did not focus specifically on accelerating the hydrolysis step, even though the degradation of this chemical oxygen demand (COD) fraction is likely to be the limiting step in many investigations of this type of wastewater. The mechanically stirred anaerobic sequencing batch biofilm reactor offers an alternative for hastening the hydrolysis step, because mechanical agitation can help to speed up the reduction of particle sizes in the fraction of particulate organic matter. In the present study, a 4.5-L reactor was operated at 30°C, with biomass immobilized on cubic polyurethane foam matrices (1 cm of side) and mechanical stirring provided by three flat-blade turbines (6 cm) at agitation rates varying from 0 to 500 rpm. The reactor was operated to treat diluted swine waste, and mechanical stirring efficiently improved degradation of the suspended COD. The operational data indicate that the reactor remained stable during the testing period. After 2 h of operation at 500 rpm, the suspended COD decreased by about 65% (from 1500 to 380 mg/L). Apparent kinetic constants were also calculated by modified first-order expressions.     

铁炭微电解-亚铁还原氧化法处理花菁废水的研究

研究了微电解-亚铁还原氧化法在处理花菁废水上的应用,结果显示,经过处理,废水色度的去除率>97%,化学需氧量(COD)的去除率>90%.研究了影响处理效果的因素,对于废水中有机物的去除、脱色以及废水可生化性的提高进行了探讨,并通过紫外-可见光谱和色质联用(GC/MS)对处理前后的废水组分进行了分析.     

Biological Treatment of Shrimp Aquaculture Wastewater Using a Sequencing Batch Reactor

To improve the water quality in the shrimp aquaculture, a sequencing batch reactor (SBR) has been tested for the treatment of shrimp wastewater. A SBR is a variation of the activated sludge biological treatment process. This process uses multiple steps in the same tank to take the place of multiple tanks in a conventional treatment system. The SBR accomplishes equalization, aeration, and clarification in a timed sequence in a single reactor basin. This is achieved in a simple tank, through sequencing stages, which include fill, react, settle, decant, and idle. A laboratory scale SBR and a pilot scale SBR was successfully operated using shrimp aquaculture wastewater. The wastewater contained high concentration of carbon and nitrogen. By operating the reactor sequentially, viz, aerobic and anoxic modes, nitrification and denitrification were achieved as well as removal of carbon in a laboratory scale SBR. To be specific, the initial chemical oxygen demand (COD) concentration of 1,593 mg/l was reduced to 44 mg/l within 10 days of reactor operation. Ammonia in the sludge was nitrified within 3 days. The denitrification of nitrate was achieved by the anaerobic process and 99% removal of nitrate was observed. Based on the laboratory study, a pilot scale SBR was designed and operated to remove excess nitrogen in the shrimp wastewater. The results mimicked the laboratory scale SBR.     

在线基体消除-离子色谱法测定墨水染料中的氯及硫酸盐

建立了一种在线基体消除的方法,采用离子色谱法测定了墨水染料中的氯和硫酸盐。样品经溶解、稀释后直接进样,在纯水的输送下依次经过DIONEX OnGuard Ⅱ P和IonPac NG1柱,在线实现了墨水样品中染料和疏水性干扰基体的去除,死时间流出的待测阴离子浓缩于阴离子交换柱IonPac AG11-HC。浓缩柱经阀切换进入离子色谱系统,以4.5 mmol/L Na2CO3-0.8 mmol/L NaHCO3作为淋洗液,流速1.2 mL/min,待测离子经IonPac AS23（4 mm×250 mm）分析柱分离,采用DIONEX DS6电导检测器检测,外标法定量。Cl－和SO2-4的线性范围分别为0.05~5.0、0.1~10.0 mg/L,相关系数分别为0.999 8和 0.999 7,加标回收率为94%~103%,相对标准偏差（n=11）小于1.0%,检出限（S/N=3）分别为0.02、0.05 mg/L。该方法用于墨水染料中氯和硫酸盐的测定,结果满意。     

Removal of COD,aromaticity and color of a pretreated chemical producing industrial wastewater: a comparison between adsorption,ozonation, and advanced oxidation processes

A wide range of products are produced in the chemical producing industry such as textile dyes, chemicals, printing dyes and chemicals, paper chemicals, electrostatic powder dyes, and optical brighteners. The aim of this study is to investigate the treatability of chemical oxygen demand (COD), aromaticity, and color in the wastewater of this sector, where highly complex chemicals are used. Most of the studies in the literature are related to the treatment of synthetically prepared dyed wastewater. This study is important as it is carried out with real wastewater and gives results of many treatment methods. In the study, COD, UV-vis absorbance, and color values were attempted to be removed from the wastewater of a chemical producing industry that was pretreated by coagulation-flocculation. The COD value of the pretreated wastewater discharged to the central treatment system was restricted as 1000 mg/L. Pretreated wastewater characterization is as follows: COD: 2117 mg/L, UV-vis absorbance values at; 254 nm: 9.91, 280 nm: 8.65, 341 nm: 12.77, 436 nm: 5.01, 525 nm: 2.24, and 620 nm: 1.59. In the study, adsorption, ozonation, and advanced oxidation processes (Fenton and persulfate oxidation) were used to remove COD and UV-vis absorbance values (aromaticity, organics, and color). The method by which the best removal efficiency was obtained for all parameters was the adsorption process using powdered activated carbon (PAC). The equilibrium PAC dose was found as 6 g/L. At this adsorbent dose, the removal efficiencies of UV-vis absorbance values were all around 99% and the efficiency of COD removal was 77%. The Langmuir isotherm constants were found to be q_max= 30.4 mg/g and K_L = 487.9 (L/mg). The COD concentration at this adsorbent dose was 486 mg/L and wastewater was suitable for discharge to the central wastewater treatment plant in that region.     

三维电极电助光催化降解直接湖蓝水溶液的研究

 以500W高压汞灯为光源,在TiO2光催化剂和电催化剂同时存在下,联合多相三维电极技术与光催化技术,对直接湖蓝5B水溶液进行了电助光催化降解的研究．实验结果表明,浓度为0．5mmol／L的直接湖蓝5B水溶液经30min的光电催化降解,其大环结构可迅速破坏,颜色可迅速褪去,色度去除率高达96．8％,COD去除率可达66．7％．考察了空气流速、光催化剂加入量、底物的初始浓度、电解槽电压、pH值、电导率、以及曝气量等因素对直接湖蓝5B脱色率及COD去除率的影响．     

Application of Functionalized DVB-co-GMA Polymeric Microspheres in the Enhanced Sorption Process of Hazardous Dyes from Dyeing Baths

Intensive development of many industries, including textile, paper, plastic or food, generate huge amounts of wastewaters containing not only toxic dyes but also harmful auxiliaries such as salts, acid, bases, surfactants, oxidants, heavy metal ions. The search for effective pollutant adsorbents is a huge challenge for scientists. Synthesis of divinylbenzene copolymer with glycidyl methacrylate functionalized with triethylenetetramine (DVB-co-GMA-TETA) resin was performed and the obtained microspheres were evaluated as a potential adsorbent for acid dye removal from dyeing effluents. The sorption capacities were equal to 142.4 mg/g for C.I. Acid Green 16 (AG16), 172 mg/g for C.I. Acid Violet 1 (AV1) and 216.3 mg/g for C.I. Acid Red 18 (AR18). Non-linear fitting of the Freundlich isotherm to experimental data was confirmed rather than the Langmuir, Temkin and Dubinin-Radushkevich. The kinetic studies revealed that intraparticle diffusion is the rate-limiting step during dye adsorption. Auxiliaries such as Na₂SO₄ (5–25 g/L), CH₃COOH (0.25–1.5 g/L) and anionic surfactant (0.1–0.5 g/L) present in the dyeing baths enhance the dye adsorption by the resin in most cases. Regeneration of DVB-co-GMA-TETA is possible using 1 M NaCl-50% v/v CH₃OH.     

Electrochemical removal of the hazardous dye Reactofix Red 3 BFN from industrial effluents

The electrochemical treatment of dyestuff from aqueous solution using an iron cell was achieved with reduction in chemical oxygen demand (COD) and color with high efficiency. Degradation of the azo dye Reactofix Red 3 BFN was carried out under different experimental conditions. Electrolysis completely decolorizes the effluent with substantial reduction in COD value. The rate kinetics during electrolysis was found to be first order. Results show that electrochemical reduction is a superior technology for treatment of dyes, as there is no simultaneous addition of anions, such as sulfate or chloride.     

2,8-二氨基-10-甲氧基-5,10-二氢磷杂吖嗪-10-氧化物的合成、诱变性及应用性能研究

10-羟基-5，10-二氢磷杂吖嗪-10-氧化物(1)经酰氯化、甲基化得到10-甲氧基-5，10-二氢磷杂吖嗪-10-氧化物(2)，2经硝化得到10-甲氧基-2，8-二硝基，5，10-二氢磷杂吖嗪-10-氧化物(3.62％)．3在Pd／C(u=0．05)存在下，用氢气还原为2，8-二氨基-10-甲氧基-5，10-二氢磷杂吖嗪-10-氧化物(4.71％)，考察了Bd／C(w=0．05)用量对氢化还原反应的影响．经过Salmonella／mammalian microsome assay测试，4表现为非诱变性，用4与乙酰J-酸作用得到新型双偶氮酸性染料(5)．5对羊毛和丝绸分别在2％与3％色度下浸染郜得到黑色染样，考察了5的上染曲线，并对染样进行了测色研究，发现该染料属于酸性蓝黑染料，其黑度优于目前市场上流行的酸性黑10B．     

Study of flocculation with PONILIT GT-2 anionic polyelectrolyte applied into a chemical wastewater treatment

This paper discusses the applications of synthetic PONILIT GT-2 anionic polyelectrolyte in conjuction with ferric sulfate in a chemical wastewater treatment viz. wastewater from ceramics manufacturing. Synthetic wastewaters with different colloid concentrations were prepared and the coagulation-flocculation process followed by sedimentation and/or filtration was studied. Variables associated with the chemical wastewater composition, mixing time, and the coagulant and flocculant dose are considered in order to appreciate the process efficiency in terms of turbidity, chemical oxygen demand (COD), and color removal. The degrees are higher for turbidity and color (> 80 %) removal respectively, and, satisfactory for COD (< 50 %). An empirical model was elaborated by a third order rotatable design 2³ type, considering ferric sulfate dose, polyelectrolyte dose, and mixing time as independent variables, while the turbidity and color removal efficiencies were chosen as optimization criteria. The empirical model was found adequate for the chemical wastewater treatment. Also, an analysis of the model was performed to find the optimal operating conditions, in order to apply this process for an efficient chemical wastewater treatment using ferric sulfate as coagulation agent and PONILIT GT-2 anionic polyelectrolyte as flocculation agent. The optimal values correspond to a ferric ions concentration of 6.093 mg/L, a polyelectrolyte dose of 0.651 mg/L, and a mixing time of 24.024 minutes for turbidity removal (95.869 %), respectively, and, to a ferric ions concentration of 6.01 mg/L, a polyelectrolyte dose of 0.69 mg/L, and a mixing time of 26 minutes for color removal (98.741 %).      

Fabrication of PANI@Fe–Mn–Zr hybrid material and assessments in sono-assisted adsorption of methyl red dye: Uptake performance and response surface optimization

In recent decades, industrial wastewater discharge containing toxic or hazardous manufactured dyes has risen tremendously, creating a serious environmental threat. A new hybrid adsorbent, [email protected]–Mn–Zr synthesized by mixing Fe–Mn–Zr metal oxide composite with polyaniline (PANI), was used to study methyl red (MR) dye removal from aqueous solution. The adsorption process was observed to be influenced by the sonication time, dose of [email protected]–Mn–Zr, and initial concentration of MR dye. At an initial MR dye concentration of 25 mg/L, 0.25 g/L of [email protected]–Mn–Zr dose, 15 min of sonication, and pH 7.0, the maximum MR dye adsorption efficiency of 90.34% was achieved. Kinetic analysis was performed using five different kinetic models, which shows that the pseudo-second-order kinetic model had the best fit among the five models. The Langmuir isotherm best fits the adsorption experiments at pH 7.0, yielding a significant MR dye uptake capacity of 434.78 mgg^?1. The most significant adsorption mechanisms that have been observed in uptake of MR dye onto [email protected]–Mn–Zr were electrostatic attraction, π-π bond interactions and hydrogen bonding. Response surface optimization study was performed for optimizing the experimental conditions from which maximum dye removal of 98.19% was obtained at contact time of 12 min, initial MR dye concentration of 15 mg/L and [email protected]–Mn–Zr dose of 0.4 g/L. Use of real wastewater and water samples suggest that there is only 6–19% reduction in the dye removal efficiency as compared to the blank or controlled experiments conducted with deionized water.     

Sequential anaerobic/aerobic treatment of dye-containing wastewaters: colour and COD removals, and ecotoxicity tests

Colour and COD removals of the azo dyes Congo Red (CR) and Reactive Black 5 (RB5) were individually evaluated in a sequential anaerobic/aerobic treatment system. Additionally, dye toxicity was assessed by using acute ecotoxicity tests with Daphnia magna as the indicator-organism. The anaerobic reactor was operated at approximately 27 °C and with hydraulic retention times of 12 and 24 h. The aerobic reactor was operated in batch mode with a total cycle of 24 h. During anaerobic step, high colour removals were obtained, 96.3% for CR (400 mg/L) and 75% for RB5 (200 mg/L). During the aerobic phase, COD effluent was considerably reduced, with an average removal efficiency of 52% for CR and 85% for RB5, which resulted in an overall COD removal of 88% for both dyes. Ecotoxicity tests with CR revealed that the anaerobic effluent presented a higher toxicity compared with the influent, and an aerobic post-treatment was not efficient in reducing toxicity. However, the results with RB5 showed that both anaerobic and aerobic steps could decrease dye toxicity, especially the aerobic phase, which removed completely the toxicity in D. magna. Therefore, the anaerobic/aerobic treatment is not always effective in detoxifying dye-containing wastewaters, sometimes even increasing dye toxicity.     

Degradation and toxicity reduction of textile wastewater using immobilized titania nanophotocatalysis

The feasibility and performance of photocatalytic degradation and toxicity reduction of textile dye (Acid Blue 25) have been studied at pilot scale in an immobilized titania nanoparticle photocatalytic reactor. UV-Vis, Ion Chromatography (IC) and chemical oxygen demand (COD) analyses were employed to obtain the details of the photocatalytic dye degradation. The effects of operational parameters such as H2O2, pH and dye concentration on the photocatalytic degradation of Acid Blue 25 were investigated. The aliphatic carboxylic acid intermediates and inorganic anions generated during the dye degradation process were analyzed. Daphnia magna bioassay has been used to test the progress of toxicity during the treatment process. Total disappearance of dye was attained. During the photocatalytic treatment process, the residual acute toxicity was reduced. The results showed that immobilized titania nanophotocatalysis capable to degradation and toxicity reduction of acid dye textile wastewater.     

Fe2O3/CNT催化湿法H2O2氧化苯酚

通过化学沉积法和热处理得到多壁碳纳米管负载Fe2O3催化剂 Fe2O3/CNT, Fe2O3的负载质量分数约为15.1%,XRD表征显示,负载的Fe2O3存在α和γ这2种晶型。考察了Fe2O3/CNT催化湿式H2O2氧化去除废水中苯酚催化性能,通过苯酚的去除率及反应过程中催化剂活性组分的溶出总量,研究了催化剂制备过程中添加聚乙烯醇对催化剂性能的影响。在苯酚和H2O2初始浓度分别为350和1 500 mg/L、催化剂投加量为1.0 g/L、温度80 ℃条件下,经过240 min的反应,苯酚去除率达100％,COD去除率为86.1％。     

半导体复合CdS/TiO2催化剂改性及冷冻-光催化组合方法应用的初步研究

采用溶胶-凝胶法制备多孔氧化钛,并耦合CdS,制备多孔耦合CdS/TiO₂催化剂.煅烧温度为700℃,CdS掺杂比例为3%时,催化剂性能较优.以太阳光为光源,考查了溴氨酸初始浓度对其降解效果的影响,并采用冷冻-光催化组合方法对较高浓度的溴氨酸废水的处理进行了初步研究.浓度为500 mg/L的溴氨酸模拟废水(其中氯化钠质量浓度为500 mg/L)经冷冻后,当成冰率为70%时,体系中冰层的Na⁺含量、总有机碳(TOC)和吸光度分别由209.88 mg/L,208.90 mg/L和8.120降至19.06 mg/L,24.80 mg/L和0.638.使用多孔耦合催化剂对该冰层融水光降解,光照6 h,褪色率和TOC去除率分别达到100%和87.04%.