钙型斜发沸石铵离子交换平衡的研究

测定了在不同pH值下人工改型所得钙型斜发沸石对NH4^ 的全交换容量、对NH4^ 的等温交换平衡曲线，进一步研究了其部分热力学特性。结果表明，钙型斜发沸石对NH4^ 交换总量随pH值的升高而降低，在pH值为7时为79．321mmol／100g，该离子交换过程可自发进行，且其选择性随温度的升高而降低。研究成果可为沸石法处理含氨氮废水的进一步研究提供一定的理论依据。     

改性斜发沸石处理高浓度氨氮废水

采用NaOH碱熔法对缙云斜发沸石进行处理,采用正交实验对碱熔法改性沸石的最佳条件进行了选择;并对改性前后的沸石进行粉末X射线衍射(XRD)、电感耦合等离子体发射光谱法(ICP-AES)和扫描电镜(SEM)表征;详细研究了所得改性沸石在氨氮废水处理中的净化性能.结果表明,处理沸石的水热温度对氨氮去除效果的影响最显著;碱熔法处理可使缙云斜发沸石转变为低硅铝比的Na-P型分子筛,它对氨氮废水的NH4+-N具有优异的吸附性能.当改性沸石投加量为5 g,对100 mL浓度为1000 mg.L-1氨氮溶液,氨氮去除率可达77.8%,改性沸石吸附NH4+-N是一快速吸附过程,且能较好地符合Langmuir吸附等温模式,偏向于单分子层的吸附.     

改性斜发沸石吸附水中氨氮的研究

研究了改性斜发沸石对水中氨氮的吸附行为，考察了pH值，氨氮初始浓度以及竞争阳离子等对钠型沸石吸附氨氮的影响，同时进行了钠型沸石的吸附动力学研究。结果表明，采用饱和氯化钠改性制备得到的钠型沸石具有较大的饱和吸附容量，受氨氮初始浓度和溶液pH值的影响，钠型沸石吸附氨氮的行为在YNH4^ =0.5时发生偏离，竞争阳离子的存在在不同程度上抑制了钠型沸石对氨氮的吸附。钠型沸石吸附氨氮的行为在YNH4^ ＝0．5时发生偏离。竞争阳离子的存在在不同程度上抑制了钠型沸石对氨氮的吸附。钠型沸石吸附氨氮速度的控制步骤是内扩散步骤，可采用Vermeulen吸附模型加以描述。     

NaCl改性人造沸石去除废水中氨氮的性能及其影响因素

采用NaCl溶液对人造沸石进行改性处理,考察NaCl溶液浓度对改性效果的影响.通过表面特征分析、静态吸附试验及吸附等温分析,进一步比较了人造沸石和改性人造沸石对氨氮的吸附去除性能.由X射线衍射(XRD)分析可知,沸石经改性后表面变粗糙,同时出现NaCl晶体特征衍射峰.试验结果表明,1.0 mol·L-1NaCl溶液对人造沸石的改性效果最佳;在沸石用量为1.0 g(50 mL废水)、氨氮浓度为10 mol·L-1、反应时间为40 min、反应温度为25℃和pH值为6.52条件下,改性人造沸石对氨氮的吸附效果最佳,去除率为96.02％.Langmuir和Freundlich吸附等温方程均可较好地拟合2种沸石对氨氮的吸附过程.改性人造沸石对氨氮的吸附饱和容量(21.46 mg·g-1)远大于人造沸石(9.03 mg·g-1).     

介质阻挡放电强化沸石处理氨氮废水

本文采用介质阻挡放电(DBD)强化沸石处理废水中的氨氮,比较了人造沸石、4A沸石分子筛、13X沸石分子筛等3种沸石对氨氮的去除效果,去除率分别为84.84%、17.54%、16.65%.DBD强化人造沸石对氨氮废水去除效果最佳,两者表现出了良好的协同去除氨氮作用.采用单因素实验和正交实验考察了放电电压、放电间距、放电频率等电气参数对氨氮处理的影响.研究结果表明,最佳实验参数为:放电间距0 mm,放电电压22 kV,放电频率14.5 k Hz,20—40目人造沸石投加量10 g·L~(-1),处理20 min,初始浓度100 mg·L~(-1)的模拟氨氮废水去除率达84.84%.在协同体系中,DBD产生的高压电场、热效应加速了离子的迁移,冲击波和超声等增加了分子、离子与沸石颗粒的碰撞几率.氨氮克服沸石表面界膜阻力的能力增加,促使沸石表面吸附的氨氮向沸石内部迁移,氨氮更易被去除.     

氨氮在天然沸石上的吸附及解吸

研究了氨氮浓度、温度、时间、共存阳离子等对氨氮在天然沸石上吸附的影响 ,比较了HCl及NaCl溶液对氨氮解吸的效果 ,初步探讨了沸石吸附氨氮后自然硝化的规律 .结果显示 ,随着氨氮浓度的增大或温度的升高 ,沸石吸附量上升 ,最大可达 1 1 5mg·g- 1 ;沸石吸附的初始阶段 (0— 8h) ,沸石吸附量随时间显著上升 ,此后趋于平缓 ;在不同阳离子共存的情况下 ,K 可使沸石吸附量降低 5 0 %以上 ;HCl溶液对氨氮解吸的效果好于NaCl溶液 ,解吸率最高可达到 6 0 % ;沸石吸附的氨氮在硝化细菌作用下可转化为硝氮 ,溶液中硝氮浓度 1 2 0h后可达 9mg·l- 1 ,在总氮中比率达到 2 7% .     

天然斜发沸石的氨氮改性吸附与化学再生

本文采用改性与化学再生方法,探索天然斜发沸石对氨氮吸附的最佳改性及化学再生条件.无机盐改性、热改性、有机改性试验结果表明,最佳改性方法为无机盐NaCl法,改性沸石吸附量较天然沸石提升了近20%,最佳NaCl浓度为1 mol·L~(-1);热改性法不能显著提高沸石的氨氮吸附容量,相反高温会破坏其结构;十二烷基苯磺酸钠改性法可以使改性沸石在其表面形成了新的阳离子吸附点,使其吸附性能提升;而十六烷基三甲基溴化铵改性沸石表面形成的是阴离子吸附点,对带正电的NH_4~+会产生排斥,导致其吸铵性能下降.化学再生试验表明,KCl溶液对铵饱和沸石的再生效果最显著,适宜再生浓度为0.1—0.2 mol·L~(-1).经KCl再生后的沸石再次通过NaCl改性,可延长沸石使用周期以及提高再生沸石的吸附能力.     

天然沸石对溶液中氨氮吸附特性的研究

为了探讨天然沸石对NH4 的吸附规律,以浙江缙云出产的粒径为2~3.2mm的天然斜发沸石为实验材料,进行吸附等温线实验和吸附动力学实验。结果表明,实验沸石对NH4 的吸附等温线符合Langmuir公式,且对氨氮吸附量的极限值为1.624mol·kg-1;实验沸石对NH4 的吸附反应符合一级动力学方程,反应速率常数为0.1882h-1。通过监测溶液中各阳离子浓度的变化,可确定沸石晶体内与NH4 进行交换的主要离子为Ca2 和Na ,二者占交换总量的96%以上;在交换反应初期,出现了由于沸石晶体中的离子在固液两相中的再分配所造成的离子交换的不等量现象。     

耐高氨氮浮萍的筛选及优势品种的生长特性

为寻找有效处理猪场废水等高氨氮废水的浮萍品种,对采集自48个国家和地区的520株浮萍品种在400 mg/L氨氮浓度废水,pH 6.6条件下进行初次筛选,在250 mg/L氨氮浓度下进行复筛,并对筛选所得品种的游离氨耐受性及SOD酶活进行测定.通过初筛获得23株存活浮萍品种,复筛获得XJ3(Landoltia punctata)、D0045(Spirodela polyrhiza)两株优势品种,其在250 mg/L氨氮浓度下蛋白质积累能力分别为2.17 g m-2 d-1、2.15 g m-2 d-1,干物质积累速率分别为4.98g m-2 d-1、4.60 g m-2 d-1,氮元素同化效率分别为11.84%、13.11%.实验表明XJ3可耐受游离氨浓度达1.31 mg/L,D0045可耐受最高游离氨浓度大于0.80 mg/L,验证性实验中,浮萍可在pH 4条件下800 mg/L氨氮废水中存活.SOD酶活性测定显示XJ3、D0045在250 mg/L氨氮胁迫环境下,SOD酶活性变化幅度较小,说明其相对于其他品种具有较强的氨氮胁迫耐受性.因此,XJ3、D0045两株优势浮萍植株可实现高氨氮废水中氮元素的有效转化,对于净化高氨氮废水具有较大潜力.     

改性沸石(Na-Y型)对Ni2+的吸附行为

将天然沸石熔融制得新型改性沸石(Na-Y型),研究Na-Y型沸石对Ni2 的吸附行为.结果表明,对Ni2 的饱和吸附量,Na-Y型沸石为31.04mg·g-1,而天然斜发沸石和Na型沸石(NaCl改性)仅为3.60mg·g-1和7.64 mg·g-1.Na-Y型沸石对Ni2 的等温吸附行为符合Freundlich方程.对溶液中Ni2 的吸附量在初始阶段(0-5h)快速上升,而后趋于平缓.共存阳离子对Na-Y型沸石吸附Ni2 的影响为:Co2 》Ca2 》Fe3 》 K .     

Ammonia removal from low-strength municipal wastewater by powdered resin combined with simultaneous recovery as struvite

• Powdered resin was employed for ammonia recovery from municipal wastewater. • Powdered resin achievedefficient ammonia removal under various working conditions. • Co-existing cations indicated competitive adsorption of ammonia. • Ammonia was recoveredby two-stage crystallization coupled with ion exchange. Low-strength municipal wastewater is considered to be a recoverable nutrient resource with economic and environmental benefits. Thus, various technologies for nutrient removal and recovery have been developed. In this paper, powdered ion exchange resin was employed for ammonia removal and recovery from imitated low-strength municipal wastewater. The effects of various working conditions (powdered resin dosage, initial concentration, and pH value) were studied in batch experiments to investigate the feasibility of the approach and to achieve performance optimization. The maximum adsorption capacity determined by the Langmuir model was 44.39 mg/g, which is comparable to traditional ion exchange resin. Further, the effects of co-existing cations (Ca²⁺, Mg²⁺, K⁺) were studied. Based on the above experiments, recovery of ammonia as struvite was successfully achieved by a proposed two-stage crystallization process coupled with a powdered resin ion exchange process. Scanning electron microscopy (SEM) and X-ray diffractometry (XRD) results revealed that struvite crystals were successfully gained in alkaline conditions (pH= 10). This research demonstrates that a powdered resin and two-stage crystallization process provide an innovative and promising means for highly efficient and easy recovery from low-strength municipal wastewater.     

城市污水厂氨气的来源及排放因子研究

通过对城市污水处理厂进行现场调查和分析,选取广州市猎德污水处理厂的格栅、沉砂池、A-B工艺的曝气池、组合交替式(unitank)生化池、污泥浓缩池及脱水机房采集气样,同时在A-B工艺的曝气池、unitank生化池及A-B工艺的沉淀池采集水样,采用模拟实验测试这些污水处理单元的氨挥发速率,并结合理论计算,研究氨气的来源和排放因子.结果表明,A-B工艺的曝气池和unitank工艺的生化池为城市污水处理厂的主要氨排放源.城市污水处理厂污水的氨气平均挥发速率为21.06μg.m-.2s-1,在此基础上计算出其氨气平均排放因子为0.28 g.m-3,其中A-B工艺曝气池的氨排放因子较高,为0.205 g.m-3;unitank生化池的氨排放因子为0.033 g.m-3;A-B工艺沉淀池的氨排放因子较低,为0.0085 g.m-3.     

含盐废水电渗析膜分离处理工艺研究

在水资源日益紧张、含盐废水排放量日益增多的大趋势下,寻求经济有效的含盐废水处理技术已成为重要的研究课题。以厦门某食品企业水产品加工腌泡环节含盐废水为研究对象。含盐废水经氨水沉淀、离子交换树脂软化处理,废水中钙镁离子被有效脱除,出水钙镁质量浓度已经降为10．4mg·L-1,达到软水水质标准。软化后的废水经4‰聚丙烯酰胺（PAM）絮凝并通过活性炭吸附,污染密度指数值（SDI）降低至0．41,完全达到膜分离装置进水水质的要求。预处理液再经电渗析膜进一步浓缩分离后,氯化钠质量浓度可由7351mg·L-1提升到78156mg·L-1,对盐分浓缩了10倍以上,达到废水和盐分的处理回收利用。本处理工艺流程简洁,药耗少、能耗低,比较适合小规模含盐废水的综合处理。     

Enhanced nitrification in integrated floating fixed-film activated sludge (IFFAS) system using novel clinoptilolite composite carrier

Novel carriers with favorable electrophilicity and hydrophilicity were prepared. Novel carriers had the capability of nitrification-enhancing. NH₄⁺-N removal efficiency of IFFAS process rose up to 20% with novel carriers. Nitrosomonadales and Nitrospirales were identified as the functional nitrifiers. The population of Nitrospirales increased by 4.51%. The integrated floating fixed-film activated sludge (IFFAS) process is an ideal preference for nitrification attributing to the longer sludge age for nitrifiers. However, as the core of this process, conventional carriers made of polymer materials usually exhibit negative charge and hydrophobicity on the surface, which is unbeneficial to nitrifying biofilm formation. In this study, novel clinoptilolite composite carriers with favorable hydrophilicity, positive charge and nitrification-enhancing capability were made and implemented in IFFAS system. In comparison with conventional carriers, the novel clinoptilolite composite carriers displayed positive charges on the surface (11.7±1.1 mV, pH 7.0) with increased hydrophilicity (surface contact angle dropped to 76.7°). The novel-carriers-based reactors achieved significantly better NH₄⁺-N removal efficiency at different influent concentrations, dissolved oxygen (DO) levels and shock loads (NH₄⁺-N removal efficiency rose up to 20% comparing with the control reactors filled with polyethylene (PE) carriers or activated sludge). High-throughput sequencing (HTS) results indicated the novel clinoptilolite composite carriers provided favorable niche for more types of bacteria, especially for Nitrosomonadales and Nitrospirales (the functional nitrifiers in the system). The population of Nitrospirales increased by 4.51% by using novel clinoptilolite composite carriers comparing with using PE carriers, which ensured enhanced nitrification process. This study was expected to provide a practical option for enhancing wastewater nitrification performance with the novel clinoptilolite composite carrier.     

微生物菌剂对不同废水的适配试验

采用15种不同的微生物菌剂,以葡萄糖配水、中药提取废水、啤酒废水、氨氮配水等为基质,分别测定了微生物菌剂的耗氧速率和厌氧比产甲烷速率,以单位菌剂对不同基质的耗氧速率和厌氧比产甲烷活性为指标,比较了各菌剂对废水的适配性.根据测定结果选择活性高的菌剂,在试验室进行了菌剂对废水的连续处理试验.结果表明,不同菌剂对同一种废水的好氧或厌氧活性不同,同种菌剂对不同废水的好氧和厌氧活性不同.废水的连续处理试验取得良好的处理效果.No.8菌剂处理葡萄糖配水,系统有机负荷最高可达(COD)10.8 g L-1d-1,COD去除率可达90%以上;采用No.10菌剂处理氨氮配水,好氧氨氮负荷可达(NH4-N )1.42 g L-1d-1,厌氧氨氮负荷可达(NH4-N )0.3 gL-1d-1,系统NH4-N 去除率可达90%以上.图2表3参8     

Enhancement of activated sludge performance on ammonium removal by clinoptilolite

This study evaluated the influence of clinoptilolite on the performance of activated sludge system shocked by high concentration of ammonium. The ammonium and chemical oxygen demand (COD) removal from the experimental reactor containing clinoptilolite and from the clinoptilolite-free control reactor was determined. The ammonium and COD removal was approximately 8 and 20% higher in the experimental reactor than in the control reactor, respectively. The removal increased with an increase in clinoptilolite concentration over the tested range up to 50?mg?L^?1. The presence of clinoptilolite resulted in the sludge flocs being more compacted with smoother surfaces and edges. Molecular biological analysis revealed that clinoptilolite increased the DNA diversity, richness, and evenness of sludge microbes. The enhanced-performance activated sludge previously treated with clinoptilolite was less influenced by the shock of ammonium than non-treated sludge in terms of the ammonium and COD removal. These results suggest that clinoptilolite enhanced the performance of activated sludge system in the removal of ammonium and COD. Amendment of activated sludge with natural zeolites may thus improve the efficiency of wastewater treatment.     

Recovery of Ni(II) from real electroplating wastewater using fixed-bed resin adsorption and subsequent electrodeposition

Resin adsorption and subsequent electrodeposition were used for nickel recovery. Treated wastewater can meet the Electroplating Pollutant Discharge Standard. The spent resin is completely regenerated by 3 BV of 4% HCl solution. 95.6% of nickel in concentrated eluent was recovered by electrodeposition. Effective recovery of high-value heavy metals from electroplating wastewater is of great significance, but recovering nickel ions from real electroplating wastewater as nickel sheet has not been reported. In this study, the pilot-scale fixed-bed resin adsorption was conducted to recover Ni(II) ions from real nickel plating wastewater, and then the concentrated Ni(II) ions in the regenerated solution were reduced to nickel sheet via electrodeposition. A commercial cation-exchange resin was selected and the optimal resin adsorption and regeneration conditions were investigated. The resin exhibited an adsorption capacity of 63 mg/g for Ni(II) ions, and the average amount of treated water was 84.6 bed volumes (BV) in the pilot-scale experiments. After the adsorption by two ion-exchange resin columns in series and one chelating resin column, the concentrations of Ni(II) in the treated wastewater were below 0.1 mg/L. After the regeneration of the spent resin using 3 BV of 4% (w/w) HCl solution, 1.5 BV of concentrated neutral nickel solution (>30 g/L) was obtained and used in the subsequent electrodeposition process. Using the aeration method, alkali and water required in resin activation process were greatly reduced to 2 BV and 3 BV, respectively. Under the optimal electrodeposition conditions, 95.6% of Ni(II) in desorption eluent could be recovered as the elemental nickel on the cathode. The total treatment cost for the resin adsorption and regeneration as well as the electrodeposition was calculated.     

Mechanistic insight into the biofilm formation and process performance of a passive aeration ditch (PAD) for decentralized wastewater treatment

• A Passive Aeration Ditch was developed to treat decentralized wastewater. • A model was developed to describe the process performance. • A high C/N ratio facilitates microbial growth but nitrification deteriorates. • A high salinity decreases both organic and nitrogen contaminants removal. Decentralized wastewater containing elevated salinity is an emerging threat to the local environment and sanitation in remote coastal communities. Regarding the cost and treatment efficiencies, we propose a passive aeration ditch (PAD) using non-woven polyester fabric as a feasible bubbleless aerator and biofilm carrier for wastewater treatment. Consideration has been first given to PAD’s efficacy in treating saline decentralized wastewater, and then to the impact of chemical oxygen demand-to-nitrogen (C/N) ratio and salinity on biofilm formation. A multispecies model incorporating the salinity effect has been developed to depict the system performance and predict the microbial community. Results showed that the PAD system had great capacity for pollutants removal. The biofilm thickness increased at a higher C/N ratio because of the boost of aerobic heterotrophs and denitrifying bacteria, which consequently improved the COD and total nitrogen removal. However, this led to the deterioration of ammonia removal. Moreover, while a higher salinity benefited the biofilm growth, the contaminant removal efficiencies decreased because the salinity inhibited the activity of aerobic heterotrophs and reduced the abundance of nitrifying bacteria inside the biofilm. Based on the model simulation, feed water with salinity below 2% and C/N ratio in a range of 1 to 3 forms a biofilm that can reach relatively high organic matter and ammonia removal. These findings not only show the feasibility of PAD in treatment of saline decentralized wastewater, but also offer a systematic strategy to predict and optimize the process performance.     

Preparation and characterization of calcium alginate-based composite adsorbents for the removal of Cd,Hg, and Pb ions from aqueous solution

Composite adsorbent materials containing calcium alginate, clinoptilolite, and coal-derived humic acid were prepared. Humic acid (HA), clinoptilolite (CL), alginate (AL), alginate-entrapped humic acid (AL/HA), clinoptilolite (AL/CL), and humic acid/clinoptilolite (AL/HA/CL) samples were characterized. The effectiveness of the samples as adsorbents for the removal of cadmium (Cd), mercury (Hg), and lead (Pb) were studied in a series of batch-adsorption experiments. For the AL, AL/HA, AL/CL, and AL/HA/CL adsorbents, uptake versus time data were evaluated using two kinetic models, a linear and a non-linear pseudo-first-order and a pseudo-second-order model. The data for each metal ion on all adsorbents showed good correspondence with the pseudo-second-order kinetic model. The equilibrium data were fitted to Langmuir, Freundlich, Dubinin–Radushkevich, and Temkin isotherm models. The results show that a non-linear method seems more appropriate for obtaining isotherm parameters. The non-linear Freundlich and Langmuir models for Pb and Hg produced a best fit with high R ² value (0.99). For HA adsorbent, the equilibrium data for Cd removal better fit to the non-linear Dubinin–Radushkevich isotherm.