Kinetic study on photocatalytic degradation of Acid Orange 52 in a baffled reactor using TiO2 nanoparticles

In this study, a baffled photocatalytic reactor was used for the treatment of colored wastewater containing the azo dye of Acid Orange 52(AO52). A study on the active species of the photocatalytic process using TiO_2 nanoparticles indicated that hydroxyl radical and superoxide have the greatest contribution to the dye degradation process respectively.Given that a level of biological oxygen demand/chemical oxygen demand(BOD5/COD) equal to 0.4 was achieved after about 5 hr from the beginning of the experiment, the reactor seems to be capable of purifying the wastewater containing AO52 dye after this time in order to discharge into a biological treatment system to continue the treatment process.The results of the liquid chromatography-mass spectrometry(LC-MS) test showed that during the first 4 hr of the experiment, with the breakdown of the azo bond, the contaminant was decomposed into the benzene annular compounds with less toxicity indicating a reduction in the toxicity of wastewater after removing the dye agent. The study on the kinetics of these reactions followed the pseudo-first-order kinetic model in all conditions and corresponded well to Langmuir–Hinshelwood model. According to the kinetic model for the simultaneous occurrence of possible pathways, the kinetic constant of production and degradation of intermediate products in optimal conditions was estimated to be between 0.0029 and 0.0391 min~(-1).     

Ultrasound enhanced heterogeneous activation of peroxydisulfate by bimetallic Fe-Co/GAC catalyst for the degradation of Acid Orange 7 in water

Bimetallic Fe-Co/GAC （granular activated carbon） was prepared and used as heterogeneous catalyst in the ultrasound enhanced heterogeneous activation of peroxydisulfate （PS, S2O8 2-） process. The effect of initial pH, PS concentration, catalyst addition and stirring rate on the decolorization of Acid Orange 7 （AO7） was investigated. The results showed that the decolorization efficiency increased with an increase in PS concentration from 0.3 to 0.5 g/L and an increase in catalyst amount from 0.5 to 0.8 g/L. But further increase in PS concentration and catalyst addition would result in an unpronounced increase in decolorization efficiency. In the range of 300 to 900 r/min, stirring rate had little effect on AO7 decolorization. The catalyst stability was evaluated by measuring decolorization efficiency for four successive cycles.     

ORC-GAC-Fe0 system for the remediation of trichloroethylene and monochlorobenzene contaminated aquifer: 1. Adsorption and degradation

Activities at a former Chemistry Triangle in Bitterfeld, Germany, resulted in contamination of groundwater with a mixture of tdchloroethylene(TCE) and monochlorobenzene(MCB). The objective of this study was to develop a barrier system,which includes an ORC(oxygen release compounds) and GAC(granular activated carbon) layer for adsorption of MCB and bioregeneration of GAC, a Fe^0 layer for chemical reductive dechlorination of TCE and other chlorinated hydrocarbon in situ. A laboratory-scale column experiment was conducted to evaluate the feasibility of this proposed system. This experiment was performed using a series of continuous flow Teflon columns including an ORC column, a GAC column, and a Fe^0 column. Simulated MCB and TCE contaminated groundwater was pumped upflow into this system at a flow rate of 1.1 ml/min. Results showed that 17%-50% of TCE and 28%-50% of MCB were dissipated in ORC column. Chloride ion, however, was not released, which suggest the dechlorination do not happen in ORC column. In GAC column, the adsorption of contaminants on activated carbon and their induced degradation by adapted microorganisms attached to the carbon surface were observed. Due to competitive exchange processes, TCE can be desorbed by MCB in GAC column and further degraded in iron column. The completely dechlorination rate of TCE was 0.16-0.18 cm^-1, 1-4 magnitudes more than the formation rate of three dichloroethene isomers. Cis-DCE is the main chlorinated product, which can be cumulated in the system, not only depending on the formation rate and its decaying rate, but also the initial concentration of TCE.     

Comparison of membrane fouling during short-term filtration of aerobic granular sludge and activated sludge

Aerobic granular sludge was cultivated adopting internal-circulate sequencing batch airlift reactor.The contradistinctive experiment about short-term membrane fouling between aerobic granular sludge system and activated sludge system were investigated.The membrane foulants was also characterized by Fourier transform infrared(FTIR)spectroscopy technique.The results showed that the aerobic granular sludge had excellent denitrification ability;the removal efficiency of TN could reach 90%.The aerobic granular sludge could alleviate membrane fouling effectively.The steady membrane flux of aerobic granular sludge was twice as much as that of activated sludge system.In addition,it was found that the aerobic granular sludge could result in severe membrane pore-blocking, however,the activated sludge could cause severe cake fouling.The major components of the foulants were identified as comprising of proteins and polysaccharide materials.     

Stability of expanded granular sludge bed process for terylene artificial silk printing and dyeing wastewater treatment

Terylene artificial silk printing and dyeing wastewater(TPD wastewater), containing averaged 710 mg/L terephthalic acid(TA) as the main carbon source and the character pollutant, was subjected to expanded granular sludge bed(EGSB) process. The stability of the EGSB process was firstly conducted by laboratory experiment. TA ionization was the predominated factor influencing the acid-base balance of the system. High concentration of TA in wastewater resulted in sufficient buffering capacity to neutralize the volatile fatty acids(VFA)generated from substrate degradation and provided strong base for anaerobic system to resist the pH decrease below 6.5. VFA and UFA caused almost no inhibition on the anaerobic process and biogas production except that pH was below 6.35 and VFA was at its maximum value. Along with the granulating of the activated sludge, the efficiency of organic removal and production rate of biogas increased gradually and became more stable. After start-up, the efficiency of COD removal increased to 57%—64%, pH stabilized in a range of 7.99—8.04, and production rate of biogas was relatively high and stable. Sludge granulating, suitable influent of pH and loading were responsible for the EGSB stability. The variation of VFA concentration only resulted in neglectable rebound of pH, and the inhibition from VFA could be ignored in EGSB. The EGSB reactor was stable for TPD wastewater treatment.     

Nitrogen removal from coal gasification wastewater by activated carbon technologies combined with short-cut nitrogen removal process

A system combining granular activated carbon and powdered activated carbon technologies along with shortcut biological nitrogen removal （GAC-PACT-SBNR） was developed to enhance total nitrogen （TN） removal for anaerobically treated coal gasification wastewater with less need for external carbon resources. The TN removal efficiency in SBNR was significantly improved by introducing the effluent from the GAC process into SBNR during the anoxic stage, with removal percentage increasing from 43.8%49.6% to 68.8%-75.8%. However, the TN removal rate decreased with the progressive deterioration of GAC adsorption. After adding activated sludge to the GAG compartment, the granular carbon had a longer service-life and the demand for external carbon resources became lower. Eventually, the TN removal rate in SBNR was almost constant at approx. 43.3%, as compared to approx. 20.0% before seeding with sludge. In addition, the production of some alkalinity during the denitrification resulted in a net savings in alkalinity requirements for the nitrification reaction and refractory chemical oxygen demand （COD） degradation by autotrophic bacteria in SBNR under oxic conditions. PACT showed excellent resilience to increasing organic loadings. The microbial community analysis revealed that the PACT had a greater variety of bacterial taxons and the dominant species associated with the three compartments were in good agreement with the removal of typical pollutants. The study demonstrated that pre-adsorption by the GAC-sludge process could be a technically and economically feasible method to enhance TN removal in coal gasification wastewater （CGW）.     

Removal of anaerobic soluble microbial products in a biological activated carbon reactor

The soluble microbial products (SMP) in the biological treatment effluent are generally of great amount and are poorly biodegradable. Focusing on the biodegradation of anaerobic SMP, the biological activated carbon (BAC) was introduced into the anaerobic system. The experiments were conducted in two identical lab-scale up-flow anaerobic sludge blanket (UASB) reactors. The high strength organics were degraded in the first UASB reactor (UASB1) and the second UASB (UASB2, i.e., BAC) functioned as a polishing step to remove SMP produced in UASB1. The results showed that 90% of the SMP could be removed before granular activated carbon was saturated. After the saturation, the SMP removal decreased to 60% on the average. Analysis of granular activated carbon adsorption revealed that the main role of SMP removal in BAC reactor was biodegradation. A strain of SMP-degrading bacteria, which was found highly similar to Klebsiella sp., was isolated, enriched and inoculated back to the BAC reactor. When the influent chemical oxygen demand (COD) was 10,000 mg/L and the organic loading rate achieved 10 kg COD/(m 3 ·day), the effluent from the BAC reactor could meet the discharge standard without further treatment. Anaerobic BAC reactor inoculated with the isolated Klebsiella was proved to be an effective, cheap and easy technical treatment approach for the removal of SMP in the treatment of easily-degradable wastewater with COD lower than 10,000 mg/L.     

Treatment of coking wastewater by a novel electric assisted micro-electrolysis filter

A newly designed electric assisted micro-electrolysis filter(E-ME) was developed to investigate its degradation efficiency for coking wastewater and correlated characteristics. The performance of the E-ME system was compared with separate electrolysis(SE) and micro-electrolysis(ME) systems. The results showed a prominent synergistic effect on COD removal in E-ME systems. Gas chromatography/mass spectrometry(GC–MS) analysis confirmed that the applied electric field enhanced the degradation of phenolic compounds.Meanwhile, more biodegradable oxygen-bearing compounds were detected. SEM images of granular activated carbon(GAC) showed that inactivation and blocking were inhibited during the E-ME process. The effects of applied voltage and initial p H in E-ME systems were also studied. The best voltage value was 1 V, but synergistic effects existed even with lower applied voltage. E-ME systems exhibited some p H buffering capacity and attained the best efficiency in neutral media, which means that there is no need to adjust p H prior to or during the treatment process. Therefore, E-ME systems were confirmed as a promising technology for treatment of coking wastewater and other refractory wastewater.     

Function of anaerobic portion in a conventional sequencing batch reactor

The performance of SBRs treating two kinds of wastewater(synthetic wastewater containing polyvinyl alcohol and effluent from a coke-plant wastewater treatment system)was investigated in this study,in order to examine the exact function of anaerobic portion in a conventional SBR.The set up of 4-or 8-hour anaerobic mixing period in a SBR's cycle did not benefit for PVA degradation.While an anaerobic reactor seeded with anaerobic sludge could partly hydrolyse and acidify PVA into readily-degradable intermediates.During the anaerobic fill period of an SBR treating the effluent from a coke-plant wastewater treatment system,the organic concentration was reduced to certain extent due to the adsorption of activated sludge and dilution of the mixed liquor from the previous cycle.Parts of readily-degradable organics in the influent were utilised by denitrifiers as carbon source.The biomass in a conventional SBR was alternatively imposed to aerobic and anaerobic conditions in its operating cycle,the environmental conditions needed for anaerobic hydrolization and acidification of refractory organics could not occur in such an SBR.     

Comparison of decolorization of reactive microorganisms isolated from various sources

Azo dyes are among the oldest man-made chemicals and they are still widely used in the textile, printing and the food industries.About 10% - 15% of the total dyes used in the industry is released into the environment during the manufacturing and usage. Some dyes and some of their N-substituted aromatic bio-transformation products are toxic and/or carcinogenic and therefore these dyes are considered to beenvironmental pollutants and health hazards. These azo dyes are degraded by physico-chemical and biological methods. Of these, biological methods are considered to be the most economical and efficient. In this work, attempts were made to degrade these dyes aerobically. Theorganisms which were efficient in degrading the following azo dyes-Red RB, Remazol Red, Remazol Blue, Remazol Violet, Remazol Yellow,Golden Yellow, Remazol Orange, Remazol Black- were isolated from three different sources viz., wastewater treatment plant, paper milleffluent treatment plant and tannery was tewater treatment plant. The efficiency of azo dye degradation by mixed cultures from each source wasanalyzed. It was found that mixed cultures from tannery treatment plant worked efficiently in decolorizing Remazol Red, Remazol Orange,Remazol Blue and Remazol Violet, while mixed cultures from the paper mill effluent worked efficiently in decolorizing Red RB, Golden Yellow and Remazol Yellow. The mixed cultures from wastewater treatment plant efficiently decolorized Remazol Black.     

Combination of adsorption and biodegradation processes for textile e uent treatment using a granular activated carbon-biofilm configured packed column system

The objective of this study was to investigate the feasibility of using a granular activated carbon-biofilm configured packed column system in the deeolodzation of azo dye Acid Orange 7-containing wastewater.The Acid Orange 7-degrading microbial from anaerobic sequencing batch reactor which treating the azo dye-containing wastewater for more than 200 d was immobilized on spent granular activated carbon(GAC)through attachment.The GAC-biofilm configured packed column system showed the ability to decolorize...     

高盐条件下染料酸性橙7的生物降解特性

对偶氮染料废水厌氧-好氧生物处理中的高盐度抑制生物活性和芳香胺自氧化问题,通过多种强化策略,考察了NaCl为100g/L时酸性橙7(AO7)的生物降解特性.结果表明,加入葡萄糖(0.5g/L)、蛋白胨(1g/L)和酵母粉(0.5g/L)有利于高盐条件下AO7的生物降解.进水中加入酸性红B对AO7的脱色有加速作用.耐盐污泥中加入蒽醌形成的蒽醌-污泥自固定化体系可以促进AO7脱色,当蒽醌浓度为100mg/L时,AO7最大脱色率约为92%.以活性炭毡作为生物载体,厌氧和好氧体系均可实现稳定运行,且体系污泥沉降性良好,脱色速率达26.67mg/(L×h),且可有效抑制脱色中间产物1-氨基-2-萘酚的好氧自氧化,使COD去除率始终保持在90%以上.     

Decolorization of Orange II using an anaerobic sequencing batch reactor with and without co-substrates

We investigated the decolorization of Orange II with and without the addition of co-substrates and nutrients under an anaerobic sequencing batch reactor (ASBR). The increase in COD concentrations from 900 to 1750 to 3730 mg/L in the system treating 100 mg/L of Orange II-containing wastewater enhanced color removal from 27% to 81% to 89%, respectively. In the absence of co-substrates and nutrients, more than 95% of decolorization was achieved by the acclimatized anaerobic microbes in the bioreactor treating 600 mg/L of Orange II. The decrease in mixed liquor suspended solids concentration by endogenous lysis of biomass preserved a high reducing environment in the ASBR, which was important for the reduction of the Orange II azo bond that caused decolorization. The maximum decolorization rate in the ASBR was approximately 0.17 g/hr in the absence of co-substrates and nutrients.     

Rapid decolorization of Acid Orange II aqueous solution by amorphous zero-valent iron

Some problems including low treatment capacity, agglomeration and clogging phenomena, and short working life, limit the application of pre-treatment methods involving zero-valent iron (ZVI). In this article, ZVI was frozen in an amorphous state through a melt-spinning technique, and the decolorization effect of amorphous ZVI on Acid Orange II solution was investigated under varied conditions of experimental variables such as reaction temperature, ribbon dosage, and initial pH. Batch experiments suggested that the decolorization rate was enhanced with the increase of reaction temperature and ribbon dosage, but decreased with increasing initial solution pH. Kinetic analyses indicated that the decolorization process followed a first order exponential kinetic model, and the surface-normalized decolorization rate could reach 2.09 L/(m². min) at room temperature, which was about ten times larger than any previously reported under similar conditions. Recycling experiments also proved that the ribbons could be reused at least four times without obvious decay of decolorization rate and efficiency. This study suggests a tremendous application potential for amorphous ZVI in remediation of groundwater or wastewater contaminated with azo dyes.     

菌株Acinetobacter sp.C-2对酸性红GR的脱色研究

近年来,生物法处理染料废水已成为国内外的研究热点。文章实验室通过梯度驯化,从土壤中分离筛选得到一株能有效脱色磺基化偶氮染料酸性红GR的菌株C-2,根据16S rDNA基因序列分析鉴定为Acinetobacter sp.。采用表面响应法(Response Surface Methodology,RSM)对菌株C-2脱色酸性红GR的主要影响因素进行了优化,实验结果表明最优条件为:接种量17.5 g/L,酸性红GR初始浓度100 mg/L,酵母粉浓度2.50 g/L,果糖浓度3.00 g/L。在该条件下,14 h内脱色率可达99%。同时,利用Haldane方程对菌株的脱色动力学进行拟合,最大脱色速率vmax、亲和常数Ks和抑制常数Ksi分别为328.33 mg/(g.h)、309.69 mg/L和1 365.83 mg/L,并且经计算,最佳脱色速率和GR浓度分别为105.91 mg/goh、650.37 mg/L。研究结果表明菌株C-2具有较高的偶氮染料脱色活性,用于实际染料废水的生物修复具有较好的应用前景。     

醌介导染料脱色菌株的分离鉴定及特性

实验分离获得1株能够利用醌化合物使磺酸化偶氮染料脱色的菌株JL,通过形态特征、16S rDNA与16S-23S区间序列分析表明,该菌株为蜡状芽孢杆菌(命名为Bacillus cereus JL).菌株JL使酸性大红3R脱色的最佳条件为葡萄糖浓度1g/L, pH值为5~7,温度30℃,接种量0.25g/L.蒽醌-2-磺酸(AQS)、蒽醌-2,6-二磺酸(AQDS)和2-羟基-1,4-萘醌(Lawsone)均能显著提高酸性大红3R的脱色速率,其中AQS的促进作用最为明显.研究发现, 0.1mmol/L AQS能够使菌株JL对2.0mmol/L酸性大红3R保持较高的脱色速率,而且能使多种偶氮染料脱色,表现出较好的底物广谱性.利用高效液相色谱-质谱鉴定了AQS介导的酸性大红3R脱色产物,表明酸性大红3R的偶氮键发生断裂, AQS在这一过程中仅起到电子传递的作用.     

真菌和细菌对染料的吸附脱色及再生能力的研究

进行了真菌和细菌共培养对染料的吸附脱色和吸附脱色能力再生的研究。结果表明，青霉菌G－1首先对偶氮染料S－119、蒽醌染料艳紫KN－B（C．I．Reactive violet 22）水溶液中染料进行快速吸附去除，菌丝对同种染料的吸附速度随菌丝培养液中葡萄糖浓度的增加而加快，吸附染料的G－1菌丝在与细菌的共培养中完成对染料的脱色降解，脱色速度受培养液中葡萄和氮源浓度影响较大，从吸附速率和完全脱色时间综合评价，以葡萄糖浓度为5g/L、酒石酸铵为20mmol/L的培养基中培养的菌丝对染料的吸附脱色效果最好，吸附在菌丝上的艳紫KN－B脱色后菌丝吸附脱色能力得到再生，菌丝对100mg/L的艳紫KN－B染料水溶液可重复处理4次。青霉菌G－1对酸性染料废水处理3h，色度去除率为75．9％，吸附染料的菌丝在与细菌共培养中完成对染料的脱色，对试验所用染料废水，菌丝的处理能力获得1次再生。     

零价铝还原处理偶氮染料活性蓝222废水

为有效处理难生物降解的碱性偶氮染料废水,以典型偶氮染料RB222(活性蓝222)为处理对象,在碱性条件下直接采用零价铝进行还原处理,并系统评价了溶液pH、反应温度以及零价铝粉投加量等因素对偶氮染料分子降解效果的影响. 结果表明:随着pH从7.00增至12.00,脱色率从62.6%升至98.4%;零价铝粉投加量从5 g/L增至50 g/L,脱色率从90.8%升至98.8%. 零价铝还原处理偶氮染料最优条件:温度为60~80 ℃,零价铝粉投加量为10~25 g/L,体系pH为11. 在该条件下,经过2 h处理,脱色率超过99%,溶液可生化性〔ρ(BOD₅)/ρ(COD_Cr)〕从0.169升至0.386,易于后续生化处理. 电喷雾电离质谱(ESI-MS)和傅立叶变换红外线光谱分析仪(FTIR)分析表明,偶氮染料中—NN—(偶氮键)被破坏,还原产物中有苯胺类小分子. 根据试验结果推测偶氮染料的还原路径:水中的质子接受零价铝表面的电子生成活性氢,活性氢攻击—NN—,将偶氮化合物还原裂解成易于生物降解的苯胺类小分子物质. 通过处理江苏某地所取得的实际印染废水,废水的可生化性从0.126升至0.388,提高明显.      

秸秆活性炭活化过一硫酸盐降解酸性橙7

将磷酸氢二铵((NH_4)_2HPO_4)作为活化剂制备秸秆活性炭(SAC),并用其活化过一硫酸盐(PMS)产生硫酸根自由基(SO_4~-·)降解偶氮染料酸性橙7(AO7).首先对活化前后的SAC进行FTIR表征,发现(NH_4)_2HPO_4活化后的SAC含氧官能团特征峰强度增强,可能有利于过一硫酸钾的活化.其次研究了活化剂浓度、SAC投加量、PMS浓度、初始pH、抑制剂对AO7降解效果的影响.结果表明,AO7脱色率随着活化剂浓度、SAC投加量、PMS浓度的增加而增加;同时在偏中性条件下,有利于SAC活化PMS脱色AO7;加入相同物质的量比(2000/1)的甲醇、叔丁醇、苯酚,55 min内AO7脱色率分别为88.4%、66.2%、13.4%,苯酚对反应抑制效果最好,表明SAC表面的硫酸根和羟基自由基在AO7脱色中起主要作用.最后通过紫外光谱扫描、气质联用(GC-MS)和TOC分析表明,AO7的偶氮键和萘环结构被破坏,生成含苯环类中间产物,最终矿化为二氧化碳和水,矿化率可达31.7%.