Degradation of Monoethanolamine in Aqueous Solution by Fenton’s Reagent with Biological Post-treatment

Alkanolamines in the wastewater from gas treating plants are not readily biodegradable. In this work, we have investigated the effectiveness of the Fenton’s reagent (H₂O₂-Fe²⁺) to treat monoethanolamine (MEA) as a model compound in simulated wastewater. Degradation studies were carried out in a jacketed glass reactor. The effects of concentrations of ferrous sulfate, hydrogen peroxide, and the pH of a solution on the rate of reaction were determined. A pH of 3 was found to be the optimum. The degradation reaction proceeds very fast at the beginning but slows down significantly at a longer time. A larger fractional degradation of the organics in solution was observed if the initial chemical oxygen demand (COD) of the feed solution was high. Gradual addition of H₂O₂ to the reaction mixture increased the COD removal by about 60% compared to one-time addition of the reagent at the beginning of the process. A rate equation for mineralization of the amine was developed on the basis of a simplified mechanistic model, and the lumped value of the rate constant for COD removal was determined. A partially degraded MEA solution as well as “pure” MEA was subjected to biological oxidation by activated sludge. The former substrate degraded much faster. The degradation rate and biomass generation data could be fitted by the Monod kinetic equations.     

农村小城镇生活和工业综合污水的达标处理工艺技术研究

针对中国乡镇企业的不断发展和城市化进程所造成的农村水生态环境污染日益严重的现状,该文作者采用动态模拟试验方法探索了农村小城镇生活和工业综合污水处理的工艺和方法。结果表明采用A/O生物处理单元和混凝沉淀处理单元相结合的污水处理工艺流程是比较适宜的,HRT 3 h和10 h分别是比较适宜的兼氧反应器和好氧反应器的水力停留时间(HRT),后续的混凝沉淀处理单元(HRT 2 h)是该类废水处理并使各项指标均达到国家排放标准的必须的保障措施。兼氧反应器(A段/anoxic)HRT 3 h、好氧反应器(O段/oxic)HRT 10 h和混凝沉淀(HRT 2 h)的组合工艺参数,可以使制药化工、印染和生活综合废水处理后出水中的主要污染物浓度分别为COD 35.8～50.5 mg/L,COD去除率可达到89.6%～92.5%,平均在90.4%;NH₃-N在1.13～10.8 mg/L,平均去除率78.2%,稳定运行后期的NH₃-N转化率甚至能够达到90%以上;SS 10.1～15.6 mg/L,SS的去除率92.2%～97.0%;色度只有0～5倍,色度去除率达到95.0%～100%;各项指标均可稳定达到污水综合排放标准(GB8978-1996)中的一级排放标准要求。     

Destruction of chloroanisoles by using a hydrogen peroxide activated method and its application to remove chloroanisoles from cork stoppers

A chemical method for the efficient destruction of 2,4,6-trichloroanisole (TCA) and pentachloroanisole (PCA) in aqueous solutions by using hydrogen peroxide as an oxidant catalyzed by molybdate ions in alkaline conditions was developed. Under optimal conditions, more than 80.0% TCA and 75.8% PCA were degraded within the first 60 min of reaction. Chloroanisoles destruction was followed by a concomitant release of up to 2.9 chloride ions per TCA molecule and 4.6 chloride ions per PCA molecule, indicating an almost complete dehalogenation of chloroanisoles. This method was modified to be adapted to chloroanisoles removal from the surface of cork materials including natural cork stoppers (86.0% decrease in releasable TCA content), agglomerated corks (78.2%), and granulated cork (51.3%). This method has proved to be efficient and inexpensive with practical application in the cork industry to lower TCA levels in cork materials.     

A new process for the management of olive oil mill waste water and recovery of natural antioxidants

The high polyphenol content of the wastewater is the major environmental problem caused by the olive mills. A pilot scale system for the treatment of the olive oil mills wastewater was developed aiming at the recovery of high added value-contained polyphenols and the reduction of the environmental problems. The treatment system consists of three main successive sections: The first one includes successive filtration stages aiming at the gradual reduction of the wastewater suspended solids up to a limit of 25 microm. The second section includes passing of the filtered wastewater through a series of adsorbent resins (XAD16 and XAD7HP) in order to achieve the de-odoring and decolorization of the wastewater and the removal/ recovery of the polyphenol and lactone content. The third section of the procedure includes the thermal evaporation and recovery of the organic solvents mixture, which has been used in the resin regeneration process, and finally the separation of the polyphenols and other organic substance contents using fast centrifuge partition chromatography. The final outcome of the whole procedure is (i) an odorless yellowish wastewater with a 99.99% reduced content in polyphenols and 98% reduced COD, (ii) an extract rich in polyphenols and lactones with high antioxidant activity and high added value, (iii) an extract containing the coloring substances of the olive fruit, and (iv) pure hydroxytyrosol.     

Performance and Kinetic Study on Bioremediation of Diazo Dye (Reactive Black 5) in Wastewater Using Spent GAC–Biofilm Sequencing Batch Reactor

Combinations of sequential anaerobic and aerobic process enhance the treatment of textile wastewater. The aim of this study was to investigate the treatment of diazo dye Reactive Black 5 (RB5)-containing wastewater using granular activated carbon (GAC)–biofilm sequencing batch reactor (SBR) as an integration of aerobic and anaerobic process in a single reactor. The GAC–biofilm SBR system demonstrated higher removal of COD, RB5 and aromatic amines. It was observed that the RB5 removal efficiency improved as the concentration of co-substrate in the influent increased. The alternative aeration introduced into the bioreactor enhanced mineralization of aromatic amines. Degradation of RB5 and co-substrate followed second-order kinetic and the constant (k ₂) values for COD and RB5 decreased from 0.002 to 0.001 and 0.004 to 0.001 l/mg h, respectively, as the RB5 concentration increased from 100 to 200 mg/l in the GAC–biofilm SBR system.     

人工土快滤滤床对耗氧有机污染物的去除机制

通过对人工土快滤系统不同组分的灭菌试验和分析滤床落干恢复过程中土壤有机质的变化 ,对城市生活污水中的耗氧有机物 (COD)进入人工土滤床后的去向进行了研究。结果表明 ,人工土滤床对污水COD的去除是生物与非生物共同作用的结果 ,生物作用机制不仅表现在布水时期的生物降解 ,更反映在滤床落干期对被截留有机物的分解作用。系统好氧与厌氧微生物的周期监测表明 ,人工土滤床对污水COD的降解作用 ,不仅有污水微生物的生物降解 ,还有土壤微生物的矿化分解作用。人工土快滤系统是以好氧生物为主导的生物过程与非生物过程的有机结合     

Optimization of Collaborative Photo-Fenton Oxidation and Coagulation for the Treatment of Petroleum Refinery Wastewater with Scrap Iron

The photo-Fenton oxidation treatment combined with a coagulation/flocculation process was investigated for removal of chemical oxygen demand (COD) from a refractory petroleum refinery wastewater. Scrap iron shavings were used as the catalyst source. A response surface methodology (RSM) with a cubic IV optimal design was employed for optimizing the treatment process. Kinetic studies showed that the proposed process could be described by a two-stage, second-order reaction model. Experiments showed that precipitation of iron ions can be utilized as a post-oxidation coagulation stage to improve the overall treatment efficiency. More than 96.9% of the COD removal was achieved under optimal conditions, with a post-oxidation coagulation stage accounting for about 30% of the removal, thus confirming the collaborative role of oxidation and coagulation in the overall treatment. A low-velocity gradient of 8.0 s^?1 for a short mixing time of 10 min resulted in optimum post-oxidation coagulation. Comparison of photo-Fenton oxidation to a standard Fenton reaction in the same wastewater showed more rapid COD removal for photo-Fenton, with an initial second-order rate constant of 4.0 × 10^?4 L mg^?1 min^?1 compared to the Fenton reaction’s overall second-order rate constant of 7.0 × 10^?5 L mg^?1 min^?1.     

The Effect of Treatment with Hydrogen Peroxide and the Mehra–Jackson Reagent on X-ray Diffraction Patterns of Clay Fractions

X-ray diffraction patterns of clay fractions from the AEL and EL horizons of pale-podzolic soil before and after treatment with 10% H₂O₂ and the Mehra–Jackson reagent in different sequences have been examined. The successive treatment with 10% H₂O₂ and then with the Mehra–Jackson reagent causes dissolution of Al-hydroxy-interlayers in pedogenic chlorites and the respective increase in the content of labile minerals because of a dramatic decrease in pH upon the treatment with hydrogen peroxide. The rate of these changes depends on the degree of chloritization of pedogenic chlorites in the initial samples. The result of the reverse sequence of the treatments of clay fractions (initially with the Mehra–Jackson reagent and then with hydrogen peroxide) is opposite: the chloritization of labile minerals becomes more intensive. It is provided by pH values that do not drop below 7.5 at any treatment stage. At particular stages, pH values favors the mobilization of Al compounds and their subsequent polymerization in the interlayer space of labile structures. We suppose that hydroxyl-aluminosilicate layers may be formed in the interlayer space upon this treatment sequence.     

Chemical pretreatment of olive oil mill wastewater using a metal-organic framework catalyst

Olive oil mill wastewaters (OOMW) are not suited for direct biological treatment because of their nonbiodegradable and phytotoxic compound (such as polyphenols) content. Advanced technologies for treatment of OOMW consider mainly the use of solid catalysts in processes that can be operated at room conditions. A system based on combined actions of catalytic oxidations and microbial technologies was studied. The wet hydrogen peroxide catalytic oxidation (WHPCO) process is one of the new emerging oxidation processes particularly attractive for the pretreatment of highly polluted OOMW containing polyphenols that are not suited for classical treatments. In this work, the biodegradability of OOMW was evaluated before and after treating the wastewater samples by the WHPCO process using a metal-organic framework (MOF) as a catalyst. This material, containing Cu and prepared with benzene-1,3,5-tricarboxylic acid (BTC), is a robust metal-organic polymer with a microporous structure that is reminiscent of the topology of zeolite frameworks.     

Operational Optimisation of Pilot Scale Biological Nutrient Removal at the Ciudad Real (Spain) Domestic Wastewater Treatment Plant

The aim of this work is optimising operating conditions for a possibleimplementation of a Biological Nutrient Removal (BNR) process in the Wastewater Treatment Plant (WWTP) of Ciudad Real (Spain). Several factors (hydraulic retention times, anaerobic nitrate concentration, sludge age and wastewater biodegradability) were tested using a pilot scale VIP (Virginia Initiative Plant) activated sludge process and domestic wastewater from the full scale plant. Hydraulic retention times used did not cause changes in N and P removal. P removal was adversely affected by anaerobic NO₃ ^- and improved with higher BOD₅/COD ratios in wastewater. Influence of sludge age was very low in P removal, but N removal was mainly affected by this factor. Final operating conditions were selected taking into account their effects over one of both nutrients. COD and SS removal were always successful. N removal was also easily reached and the main difficulty was P removal. P sludge content was very low (2.5–4%) approximately and was also affected by the same factors tested. The main factor to improve P removal was supposed to be the organic wastewater composition. Wastewater characteristics were modified by using different sources from the WWTP. Volatile fatty acids (VFA) addition to the wastewater by using supernatant of the anaerobic sludge digesters seemed to be the best practical solution for a future BNR implementation in the WWTP.     

Hydraulic Retention Time Influence on Improving Flocculation in the Activated Sludge Processes Through Polyelectrolytes

Hydraulic retention time (HRT) influence improving sludge flocculation with adding the polyelectrolytes (non-ionic, anionic, and cationic) was studied on an activated sludge (AS) system fed with synthetic domestic wastewater (SDW), dairy industry wastewater (DIW), and caramel industry wastewater (CIW). The sludge volumetric index, food/microorganism ratio (F/M), and mixed liquor volatile suspended solids at different HRTs (6, 8 and 10 h) were monitored on an experimental model. Results showed that both SDW and IW had the best sludge flocculation conditions at 8 h and 100 mL of non-ionic polyelectrolyte (0.2 mg L^?1). In addition, this phenomenon reached the organic matter removal efficiencies of 95.9, 95.7, and 94.2% for SDW, DIW, and CIW, respectively. Therefore, optimum HRT increased the organic matter removal efficiencies by 10%, sludge concentration by 37% (22–55%), and F/M ratio by 70%. Moreover, the polyelectrolytes used in AS improved the sludge flocculation by 2.9 times.     

厌氧流化床净化畜禽废水与产电性能

为实现从畜禽废水处理中回收能源,先后以厌氧沼液、低浓度畜禽原水及高浓度畜禽原水作为进水,利用厌氧流化床双室微生物燃料电池(anaerobic fluidized bed microbial fuel cell,AFB-MFC)进行微生物产电及有机物去除研究,重点考察氨态氮质量浓度及COD(化学需氧量)容积负荷对系统COD去除率及产电性能的影响。结果表明:以稀释后的沼液作为进水时,当氨态氮质量浓度达到387.6mg/L时,氨态氮对产电微生物产生明显的短期抑制,产电量下降7.0%,但经过5d的适应期后,系统产电恢复到原来的水平。以畜禽原水作为进水时,系统COD容积负荷在12d内由2.3kg/(m3·d)提升至14.9kg/(m3·d)时,COD去除率保持在74.5%～88.1%;随着容积负荷的提升,系统产电量上升,但上升幅度较小,最高输出电压为379.3mV,相应的面积功率密度为74.9mW/m2;由于进水pH值的差异,高浓度畜禽原水最高输出电压较低浓度畜禽原水低21.4mV;AFB-MFC系统内阻较低,仅为48.5Ω,此时功率密度为75.6mW/m2。本装置实现了畜禽废水的高效处理,同时获得电能,为其资源化处理提供新途径。     

Improved combined chemical and biological treatments of olive oil mill wastewaters

A novel system was investigated, finalized to reduce the impact of highly polluting wastewaters, and based on combined actions of catalytic oxidations and microbial biotechnologies. Olive oil mill wastewaters (COD 10,000-100,000 mg O(2)/L) were oxidized up to 80-90% by stoichiometric amounts of dilute hydrogen peroxide (35%) and in the presence of water soluble iron catalysts, either Fe(II) or Fe(III), at concentrations up to 1% w/w and more, i.e., much larger than those reported for conventional Fenton processes. In the combined action, the mineralization activity of a selected microbial consortium was used to degrade residual volatile and nonvolatile organic compounds into CO(2) and biomass. The results of this search could suggest an improved operational methodology capable to reduce the potential impact of wastewater.     

毛管逆滤渗污水净化反应器原理研究及室内试验验证

污水回用是解决城市缺水问题的一条有效途径。该文提出了一种新方法，尝试利用多孔介质毛细管作用过滤生活污水。制造了4个毛管逆滤渗污水净化器，采用普通河砂作为过滤介质进行了室内试验。试验采用两个因素：水势差、滤池内外径比。水势差选取4个水平：0.11、0.26、0.41、0.56 m，外层与内层水池直径比选取3个水平：14/6、12/6、10/6，以研究利用毛细管作用净化污水的可行性，并定量确定水势差及内外层水池的相对大小对该系统运行效果的影响。用反应器去除污水COD的多少来评价过滤效果。结果表明，过滤速度及净化效果与水势差之间呈极显著的对数相关关系，两者都随着水势差的增大而提高。当水势差为0.56 m时，COD的去除率可高达80%左右，过滤速度可以高达0.15 m/h。外层与内层水池的直径比(D/d)越大滤速越小,但该比值对COD的去除率无明显影响。该装置在运行过程中，污水被过滤介质所覆盖，有效地避免了污水的刺激性气味和蚊蝇孳生对周边环境的影响。     

猪场废水厌氧消化液后处理技术研究及工程应用

猪场废水经过厌氧消化后，可生化性变差，BOD₅/COD仅为0.19，并且碳、氮倒置，比例严重失调，给后续好氧处理带来很大困难。采用序批式活性污泥法(SBR)工艺直接处理厌氧消化液，污染物的去除效果很差，COD仅去除8.31%，NH₃-N去除78.7％。通过改善厌氧消化液的可生化性和培养高效脱氮菌种等措施，COD、NH₃-N去除率改善显著，COD、BOD₅与SS的去除分别达到89.6%～93.4%、97.9%，95.6%，特别是对NH₃-N，达到了99%以上去除效率。将实验室结果应用于实际工程，也取得了好的效果，工程上SBR系统对猪场废水厌氧消化液的COD去除90%左右，出水COD基本上在300 mg/L以下。NH₃-N去除率大于99%，出水NH₃-N小于10 mg/L。BOD₅去除率大于98%，出水BOD₅小于20 mg/L。TN去除率大于90%。     

Fe3+和Na+共存对缺氧污泥脱氮除磷效率和胞内外聚合物的影响

为了提高多种金属离子共存的含盐废水脱氮除磷效率和生物絮凝性,考察Fe^3+和Na^+共存对A2O工艺缺氧区污染物去除率的影响,研究缺氧区胞内聚合物(Intracellular Polymeric Substances,IPS)和胞外聚合物(Extracellular Polymeric Substances,EPS)的变化,采用气相色谱法与蒽酮比色法分析IPS中聚-β-羟丁酸(Poly-β-hydroxybutyrate,PHB)和糖原含量的变化,结合三维荧光光谱(Three-dimensional Excitation Emission Matrix Fluorescence Spectroscopy,3D-EEM)与傅里叶变换红外光谱(Fourier Transform Infrared Spectroscopy,FTIR)探索EPS组成结构的变化,以期揭示共存的Fe^3+和Na^+、IPS及EPS与污泥絮凝性的关系。结果表明:1)单一Fe^3+的加入有助于提高COD、TN和TP的去除率,增加碱性磷酸酶与酸性磷酸酶活性,IPS和EPS总量增多。2)在Fe^3+和Na^+共存的条件下,当Fe^3+浓度为10 mg/L、Na^+浓度为0.5 g/L时,低浓度的Na^+提高了COD、TN和TP去除率,增强了碱性磷酸酶与酸性磷酸酶活性,增加了IPS总量,但是抑制了微生物EPS的分泌,EPS总量下降;当Fe^3+为10 mg/L,Na^+浓度(>1 g/L)继续升高时,高浓度的Na^+导致COD、TN和TP去除率下降,IPS总量降低,但是促进了微生物EPS的分泌,EPS总量增加。3)由FTIR分析可知,Fe^3+和Na^+浓度的变化并未导致松散结合型胞外聚合物(Loosely Bound Extracellular Polymeric Substances,LB-EPS)和紧密结合型胞外聚合物(Tightly Bound Extracellular Polymeric Substances,TB-EPS)的官能团发生明显变化,主要成分始终为蛋白质(Protein,PN)和多糖(Polysaccharide,PS);由3D-EEM分析可知,Fe^3+的加入使三维荧光光谱中出现了可见区类色氨酸峰,Na^+的加入使色氨酸、腐殖酸类物质降解,EPS的成分改变。4)IPS和EPS之间存在竞争生长,IPS/EPS比值较高时,IPS占主导作用,污泥絮凝性能好。     

Treatment of olive oil mill wastewater by Fenton's reagent

Wastewater from olive oil mills has been treated by means of the Fe(II)/H(2)O(2) system (Fenton's reagent). Typical operating variables such as reagent concentration (C(H(2)O(2)) = 1.0--0.2 M; C(Fe(II)) = 0.01--0.1 M) and temperature (T = 293--323 K) exerted a positive influence on the chemical oxygen demand and total carbon removal. The optimum working pH was found to be in the range 2.5--3.0. The exothermic nature of the process involved a significant increase of the temperature of the reaction media. The process was well simulated by a semiempirical reaction mechanism based on the classic Fenton chemistry. From the model, the reaction between ferric iron and hydrogen peroxide [k = 1.8 x 10(15) exp((-12,577 +/- 1248)/T)] was suggested to be the controlling step of the system. Also, the simultaneous inefficient decomposition of hydrogen peroxide [k = 6.3 x 10(12) exp((-11,987 +/- 2414)/T)] into water and oxygen was believed to play an important role in the process. On the basis of stoichiometric calculations for hydrogen peroxide consumption, an estimation of the process economy has been completed.     

絮凝预处理对奶牛场膜生物反应器膜污染影响的中试试验

为探讨经济实用的高浓度奶牛场污水预处理方法,该研究开展了絮凝预处理对膜生物反应器（Membrane Bioreactor,MBR）膜污染的影响试验,试验采用高浓度奶牛场污水原水和絮凝出水作为MBR进水依次运行,对比分析了不同进水的膜污染规律及其原因。结果表明,絮凝出水作为MBR进水时膜污染速率较污水原水降低47%且膜组件的维护性清洗时间间隔由10 d延长至16 d;MBR处理污水原水的膜池混合液中胞外聚合物（Extracellular Polymeric Substances,EPS）和溶解性微生物产物（Soluble Microbial Products,SMP）浓度分别为4.76和3.94 g/L,而处理絮凝出水时的EPS和SMP浓度值分别为3.97和2.23 g/L。两阶段MBR膜池混合液各粒径值总体上均呈现先增大后减小的趋势,第1和第2阶段的最大粒径体积百分比分别出现在第16天和第23天,第1阶段EPS浓度和SMP浓度均随着颗粒粒径的增大而减小,第2阶段EPS浓度随着颗粒粒径的增大而增大但SMP浓度与颗粒物粒径之间无变化规律;MBR处理污水原水的膜池混合液颗粒粒径的峰值较分散,且16 d后峰值向小粒径方向移动,而处理絮凝出水的峰值粒径相对稳定,且峰值粒径对应的最大体积百分比从3.57%增加至5.95%。MBR对2种进水的化学需氧量（Chemical Oxygen Demand,COD）去除率均可达90%以上,氨氮（Ammonia Nitrogen,NH3-N）去除率均接近90%,对絮凝出水的总磷（Total Phosphorus,TP）处理效果高于污水原水。絮凝预处理使膜池混合液的EPS和SMP浓度降低且SMP蛋白质浓度显著降低（P<0.05）、膜池混合液颗粒粒径显著增加（P<0.05）,有效减缓了MBR的膜污染,絮凝预处理与MBR组合可望为高浓度奶牛场污水处理提供可靠的技术途径。     

牛场废水培养肥壮蹄形藻的工艺参数优化

该研究选用肥壮蹄形藻（Kirchneriella obesa）为试验藻种,以秸秆过滤后牛场废水与BG11培养基的混合物为微藻培养液,在前期单因素试验基础上研究废水添加比、光照强度、光照时间和通气量对微藻干重、氨氮去除率、总磷去除率和Chemical Oxygen Demand (COD)去除率的交互影响,通过Central Composite Design (CCD)中心组合试验得到了相应的影响模型。试验结果表明牛场废水培养肥壮蹄形藻的最优工艺条件为：废水添加比例26%、光照强度9 028 lx、光照时间21.5 h、通气量2.0 L/min。该研究采用优化工艺,在14d的培养周期末期,肥壮蹄形藻的干重达到了1.141g/L,废水中氨氮去除率、总磷去除率和COD去除率分别达到了99.65% 、99.15%、85.83%,响应值指标的预测值和实际值误差均在2%以内。各因素对目标值的交互作用关系为：废水添加比例和光照时间对肥壮蹄形藻干重的交互作用较强,废水添加比例和通气量对肥壮蹄形藻培养液中氨氮去除率、总磷去除率和COD去除率均具有较强的交互作用,而光照强度和光照时间仅对总磷去除率具有较强的交互作用。该研究为牛场废水培养微藻的工业化生产提供了理论参考。     

Demonstration of pectic polysaccharides in cork cell wall from Quercus suber L

Scanning electron microscopy (SEM) and chemical analysis were used to observe the cell wall changes that occur in cork with "mancha amarela", when compared to a standard cork. To mimic the microbial attack exhibited in cork with mancha amarela, the standard cork was treated enzymatically with commercial pectinase and hemicellulase preparations. The tissues treated with pectinase were comparable with those attacked with mancha amarela. Both were composed by deformed and wrinkly cells and exhibited cell wall separation at the middle lamella level, which suggests solubilization/removal of the pectic polysaccharides. The cork cell wall material, prepared as alcohol-insoluble residue, was fractionated by hot water (Pect(H)()2(O)) and hot dilute acid (Pect(acid)). The relatively large amount of hexuronic acid and the occurrence of Ara in the SPect(H)()2(O) and SPect(acid) allow to confirm, as far as we know, for the first time the presence of pectic polysaccharides in the cell walls of cork from Quercus suber L. They accounted for ca. 1.5% of the cork and may consist of polymers with long side chains of arabinosyl residues. These polymers have to be taken into account in any realistic model of the cork cell wall. Cork with mancha amarela contained a smaller amount of pectic polysaccharides (ca. 0.5%), which confirms that the cellular separation observed by SEM is related to the degradation/removal of the middle lamella pectic polysaccharides.