人工湿地中沸石对铵吸附能力的生物再生研究

利用铵吸附饱和的天然斜发沸石和沙质土壤作为基质,构建了沸石柱和芦苇、菖蒲沸石人工湿地试验系统,采用曝气供氧、自然复氧、植物根系输氧以及培养系统中基质上的硝化菌群的方法,研究了铵吸附饱和的沸石在沸石柱和湿地中的生物再生过程。结果显示,沸石在湿地中再生过程符合指数模拟,在试验周期内沸石在沸石柱中再生可以用指数和线性模拟。沸石在湿地系统和沸石柱中经过1个月的再生,交换容量分别恢复到了原来的60.3%~62.6%和11.8%,3个月后分别恢复到了原来的94.6%~94.8%和38.4%。试验证明,沸石在湿地中再生比在沸石柱中再生效果好,交换容量恢复率高出约50%~63%。根据试验结果,探讨了铵吸附饱和的沸石在人工湿地中的生物再生机理,证明了饱和沸石在湿地中生物再生的可行性。     

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.     

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.     

天然沸石对农田退水中氨氮的去除

利用静态吸附实验研究了沸石颗粒大小、氨氮初始浓度、接触时间及Na+离子浓度等因素对天然白银沸石去除模拟黄灌区农田退水中氨氮(NH4+-N)效果的影响,同时研究了吸附等温线特征,并考察了其吸附机理.研究结果表明,沸石颗粒大小、接触时间及NH4+和Na+初始浓度对NH4+-N交换容量都会产生一定影响;根据复相关系数(R2),NH4+-N的吸附等温线更符合三参数等温线模型;而对于两参数等温线模型,Langmuir模型比Freundlich模型能更好地描述NH4+-N在天然沸石上的离子交换过程;NH4+-N吸附实验数据与Elovich模型拟合最好(R2≥0.9766).研究结果表明了天然白银沸石是一种适合NH4+-N去除的离子交换剂,可用于黄灌区农田退水中NH4+-N的去除.     

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。     

阳离子表面活性剂用量对改性沸石吸附铬酸根的影响

用不同量阳离子表面活性剂十六烷基三甲基溴化铵(CTAB)对天然沸石改性,并制备不同改性程度的改性沸石,测定沸石对CTAB的吸附量,比较几种沸石对铬酸根的吸附性能及其与改性沸石胶体Zeta电位的关系,探讨沸石对铬酸根的吸附机制及沸石再生后对铬酸根的吸附能力.结果表明,随着CTAB加入量的增加,它在沸石表面的吸附量显著增加,制备的改性沸石对铬酸根吸附性能显著提高.改性后沸石胶体的Zeta电位由负变正,而且随着CTAB用量的增加,Zeta电位正值增加.铬酸根在改性沸石表面的吸附量随离子强度增加而减小,而且改性沸石吸附的铬酸根大部分可以被中性盐解吸,说明铬酸根的吸附以静电作用机制为主.改性剂用量在0.15～0.3 mol·kg-1范围内,改性沸石再生后仍对铬酸根有很好的吸附性能,可以循环使用.     

人工湿地不同基质对氨氮的吸附特性研究

过量氮是引发水体富营养化的重要原因之一,氮的去除是控制水体富营养化的关键,其中人工湿地中基质对氨氮的去除是人工湿地处理污水的重要途径。通过基质氨氮吸附动力学、等温吸附以及基质饱和吸附后氨氮解吸实验,研究沸石、红泥、水洗砂、炉渣4种人工湿地基质净化氨氮的效果,评价其饱和吸附后氨氮解吸可能造成的二次污染风险及基质去除氨氮的主要途径。结果表明：4种基质对氨氮的吸附量顺序依次为沸石〉红泥〉炉渣〉水洗砂;沸石去除氨氮的途径以离子交换为主,物理吸附作用很小;炉渣的离子交换作用和物理吸附作用效果相当。从氨氮的解吸率来看,沸石的解吸率最小,红泥次之,炉渣和水洗砂的解吸率较大。综合评价,沸石更适合作为人工湿地污水去除氨氮的基质。     

镧-四氧化三铁-沸石复合材料制备及去除水中磷酸盐和铵

采用La3+、Fe~(2+)、Fe3+和粉末状天然沸石制备了一种镧-Fe_3O_4-沸石复合材料,通过批量吸附实验考察了该复合材料对水中磷酸盐和铵的吸附作用.结果表明,镧-Fe_3O_4-沸石复合材料对水中磷酸盐和铵的单位吸附量随吸附剂投加量的增加而降低,对磷酸盐和铵的去除率随吸附剂投加量的增加而增加.当溶液pH值由6逐渐增加到11时,镧-Fe_3O_4-沸石复合材料对水中磷酸盐和铵的吸附能力逐渐下降.镧-Fe_3O_4-沸石复合材料对水中磷酸盐的吸附平衡数据可以采用Langmuir、Freundlich和Dubinin-Redushkevich(D-R)等温吸附模型加以拟合,对铵的吸附平衡数据可以采用Langmuir和D-R等温吸附模型加以拟合.根据Langmuir模型计算得到的镧-Fe_3O_4-沸石复合材料对水中磷酸盐和铵的最大单位吸附量分别为12.9 mg·g~(-1)(以磷计)和6.99 mg·g~(-1)(以铵计).镧-Fe_3O_4-沸石复合材料对水中磷酸盐和铵的吸附动力学过程可以采用准二级动力学方程加以描述.升高反应温度增强了镧-Fe_3O_4-沸石复合材料对水中磷酸盐和铵的吸附.溶液存在的氯离子、硫酸根离子和碳酸氢根离子对镧-Fe_3O_4-沸石复合材料吸附磷无负面影响.溶液存在的钾离子对镧-Fe_3O_4-沸石复合材料吸附铵的负面影响最大,其次为钠离子,钙离子的负面影响最小.1 mol·L~(-1)NaOH溶液可以使50%左右吸附到吸附剂上的磷酸盐解吸下来.1 mol·L~(-1)NaCl溶液可以使98%左右吸附到吸附剂上的铵解吸下来.当溶液pH值为7时,镧-Fe_3O_4-沸石复合材料对磷酸盐的吸附机制主要是配位体交换作用.镧-Fe_3O_4-沸石复合材料对铵的吸附机制主要是阳离子交换作用.     

壳聚糖改性沸石吸附废水中的苯酚

开发新型低成本苯酚吸附剂是含酚废水处理技术的重点.采用90%脱乙酰度壳聚糖制备改性沸石,在与天然沸石对比的基础上,研究了改性沸石去除废水中的效果.并对影响去除率的主要因素,包括壳聚糖与斜发沸石质量比、废水pH值,吸附时间,改性沸石用量,苯酚的质量浓度等进行研究.通过正交试验确定吸附废水中苯酚最佳工艺条件是:壳聚糖与沸石质量比为1∶20.沸石-壳聚糖颗粒吸附剂用量为12 g·L-1,废水中苯酚质量浓度不大于40mg·L-1,pH值为4～6,吸附平衡时间为35 min,苯酚去除率为90%;吸附适合用Langmuir吸附等温方程来模拟.     

浅水体浮萍污水净化系统的除氮途径

以稀释的猪场厌氧污水为供试水样,少根紫萍为供试生物材料,对夏、冬2季浅水体浮萍污水净化系统TN、NH4 -N和NOx--N(NO2--N与NO3--N之和)的去除途径进行了试验研究。结果表明,在夏季气温条件下,TN通过气态氨挥发、浮萍系统吸收/吸附NH4 -N和NOx--N得以去除,3途径去除的N分别占TN去除量的30.5%、15.9%和53.6%;NH4 -N通过气态氨挥发、浮萍系统吸收/吸附和硝化反应得以去除,3途径去除的N分别占NH4 -N总去除量的33.1%、17.3%和49.6%;NOx--N则完全通过浮萍系统吸收/吸附得以去除。在冬季气温条件下,TN通过气态氨挥发和浮萍系统吸收/吸附NH4 -N得以去除,2途径去除的N分别占TN去除量的31.7%和68.3%;NH4 -N通过气态氨挥发、浮萍系统吸收/吸附和硝化反应得以去除,3途径去除的N分别占NH4 -N总去除量的28.9%、69.5%和1.6%;而水体中的NOx--N含量始终保持稳定。     

Verhalten von Nanosilber in Kläranlagen und dessen Einfluss auf die Nitrifikationsleistung in Belebtschlamm

Background, aim and scope The application of nanosilver is increasing. Knowledge on the fate and behavior of nanosilver in wastewater and wastewater treatment plants is scarce. Studies under real world conditions are completely lacking. We studied (1) the impact of nanosilver on the nitrification of sewage sludge, (2) quantified the mass flow of nanosilver in a pilot-plant, and (3) verified the mass balance in a full-scale municipal wastewater treatment plant where nanosilver is introduced to the municipal plant by an indirect discharger. Materials and Methods The addition of four different nanosilver additives on ammonia oxidation in activated sludge has been studied in batch-reactors at two concentrations (1, 100?mg/L Ag) with two exposure times (2?h, 6?days). The pilot-plant treating 70 population equivalents of domestic wastewater is operated with a 12?day sludge age. Nanosilver was applied to the activated sludge tank within two sludge ages. The silver concentrations were measured in sludge and effluent samples during dosing and the following two sludge ages. The adsorption and speciation of silver particles has been analyzed using scanning electron microscopy (SEM) coupled with energy dispersive X-ray spectroscopy (EDX). Influent, effluent and sludge were sampled on a full-scale plant (60?000 equivalent inhabitants) and analyzed for silver. Results Silver nitrate, metallic nanosilver, nano-scaled silver chloride and microcomposite silver did not show any effect on ammonia oxidation after the addition of 1?mg/L Ag to the activated sludge (corresponding to 250?mg Ag per kg solids). In contrast, 100?mg/L Ag inhibited the nitrification process by 100?% after the addition of silver nitrate and 20–30?% after addition of colloidal polymer-coated nanosilver. A complete mass balance of the pilot-plant, a steady-state system with known fluxes, demonstrates significant enrichment of silver in the sewage sludge (96?%) after the addition of silver chloride to the plant and small losses of silver into the secondary effluent (4?%). The mass fluxes are similar to metallic colloidal nanosilver investigated under the same conditions. The mass balance has been consistently confirmed by the full-scale study in a municipal wastewater treatment plant. The silver fluxes correspond to the fluxes of the suspended solids in sludge and effluent. Overall, it is estimated that from public wastewater treatment plants about 4–40?mg/a Ag per inhabitant equivalent are discharged annually to the receiving water. The analysis by SEM-EDX demonstrates adsorption and incorporation of nanosilver on biological flocs. This method yields first insight into complex building and transformation of silver associated with sulfide after adding metallic nanosilver and silver chloride to wastewater. Discussion Silver ions released from nanosilver react immediately with large amounts of chloride present in wastewater to form silver chloride. Silver ions may react with organic ligands or sulfide groups additionally. Consequently, even silver nitrate added with 1?mg/L Ag (250?mg Ag/kg TS) to activated sludge did not inhibit nitrification activity. Very high amounts of nanosilver, i.?e. 100?mg/L Ag, overburdened the system and equilibrium condition between silver ion release and ligands was not reached. The mass balance reflects the excellent attachment of nanosilver to activated sludge and biological flocs. Therefore, the main elimination process of nanosilver is attachment to the activated sludge. The elimination of nanosilver is high compared to organic and inorganic micro pollutants omnipresent in wastewater. Any further reduction of suspended solids in the effluent water will reduce the silver load. Conclusions Generally, in wastewater nanosilver occurs bonded to activated sludge flocs and therefore the elimination of nanosilver is efficient under operation conditions typical for wastewater treatment plants. The major fraction of nanosilver is removed from the system by the excess sludge withdrawal. Nonetheless, the efficiency may be further improved by a tertiary filtration step. All analyses of influent, effluent and sludge confirmed that silver exists as silver sulfide. Due to a negligible water solubility of this silver species, silver ions are not subsequently released. Recommendations and perspectives Nanosilver research should be driven to the identification of transformation processes in real environmental matrices and the influence of coatings on the adsorption behavior. There is no need for action to take special measures for nanosilver removal in the area of municipal wastewater treatment plants compared to ubiquitous hazardous organic pollutants may present in wastewater. Nevertheless, source control measures following the precautionary principle should be performed.     

活性污泥吸附预处理重油裂化制气废水

利用剩余活性污泥对含有高浓度芳香族化合物的重油裂化制气废水进行预处理的研究并提出了合适的吸附条件。结果表明，活性污泥吸附预处理对COD和悬浮物有明显的去除效果，而且可以提高废水BOD5／COD的比值，另外还有降解芳香族化合物的作用，使进入生物处理系统的废水的可生物降解性有明显的改善。这一方法为利用普通废水生物处理系统中产生的剩余活性污泥来预处理难降解的工业废水提供了一条有效的途径。     

活性炭的光催化再生机理

通过研究催化剂的改性、再生温度、外加氧化剂对活性炭光催化再生反应速度的影响,结合光催化与活性炭的吸附理论,分析了活性炭的光催化再生机理．研究表明,活性炭的光催化再生由三个准一级反应组成．再生初期,再生反应速度由TiO2光催化降解吸附质的速率决定;反应的第二个阶段由光催化反应速度和吸附质的解吸速度共同决定;再生后期,再生反应速度由吸附质在活性炭上的解吸速率所决定．活性炭表面及其大孔内负载的Ti0：是使苯酚降解转化分解为无机物的降解中心．正是由于降解中心的存在及其表面苯酚浓度趋于零的状态,使得已吸附于活性炭孔内的苯酚不断向这个中心扩散,形成活性炭孔内苯酚的浓度差．在浓度差的作用下,扩散作用持续进行,导致活性炭内吸附位的逐步空出,从而实现活性炭的光催化再生．     

废水生物脱氮中N_2O和NO_x的产生和作用

废水生物脱氮中N2O和NOx来源于硝化、反硝化、厌氧氨氧化和化学反硝化等过程.电子受体和供体浓度、pH、缓冲剂类型、有机负荷、微生物种类及其相互作用等都会影响这些气态中间产物的产生.NO2能够氧化氨和强化好氧和厌氧氨氧化,NO能够阻止C2H2对好氧氨氧化活性的抑制,两者对好氧氨氧化活性的恢复至关重要.所有这些表明,废水生物脱氮的气态中间产物N2O和NOx在氮的生物转化中具有重要的正面作用,甚至必不可少.基于NO2曝气技术和Brocadiaanammoxidans与Nitrosomonas协同作用的废水生物脱氮新技术开发是今后一段时间的重要研究方向.图4参35     

固定化菌藻系统及对污水中氮磷营养盐的净化效果

利用海藻酸钙分别包埋固定小球藻、活性污泥及其两者混合物.研究固定态小球藻与悬浮态小球藻对污水中氮磷营养盐的处理效果,实验结果表明固定态藻对氮磷的去除效果明显优于悬浮态藻,其原因主要由于海藻酸钙凝胶对氮磷的吸附,系统pH值提高引起氨的气提及磷酸盐的沉淀作用.研究固定化藻、同定化活性污泥及共固定化菌藻分别对污水中氮磷营养盐的处理效果,在同等条件下,固定化菌藻对氮磷的去除效果优于固定化活性污泥和固定化藻类.这项研究显示菌藻共生在污水处理中具有较大的潜力.     

COD对颗粒污泥厌氧氨氧化反应性能的影响

研究了COD对颗粒污泥厌氧氨氧化反应的影响,并对颗粒污泥的厌氧氨氧化脱氮性能进行了分析.厌氧颗粒污泥取自实验室长期运行的EGSB生物脱氮反应器,实验用水为人工配水,以葡萄糖为有机碳源;主要考察了COD对NH4 -N、NO2--N、NO3--N和TN去除的影响.结果表明:当进水不含COD时,反应器对NH4 -N、NO2--N和NO3--N和TN的去除率分别为12.5%、29.1%、16.1%和16.3%;当COD浓度分别为200mg/L、350mg/L和550mg/L时,反应器对NH4 -N的去除率分别为14.2%、14.2%和23.7%,对NO2--N的去除率均接近100%,对NO3--N的去除率分别为94.5%、86.6%和84.2%,对TN的去除率分别为50.7%、46.9%和50.4%,COD去除率分别为85%、66%和60%.分析发现,在反应初期,氨氮的去除主要通过厌氧氨氧化过程实现,随着反应的进行,反硝化菌活性逐渐提高,传统的反硝化过程占优势.同时还观察到,在反应初期COD对氨氮去除的抑制作用非常明显.图2参21     

A syntrophic propionate-oxidizing microflora and its bioaugmentation on anaerobic wastewater treatment for enhancing methane production and COD removal

Methane fermentation process can be restricted and even destroyed by the accumulation of propionate because it is the most difficult to be anaerobically oxidized among the volatile fatty acids produced by acetogenesis. To enhance anaerobic wastewater treatment process for methane production and COD removal, a syntrophic propionate-oxidizing microflora B83 was obtained from an anaerobic activated sludge by enrichment with propionate. The inoculation of microflora B83, with a 1:9 ratio of bacteria number to that of the activated sludge, could enhance the methane production from glucose by 2.5 times. With the same inoculation dosage of the microflora B83, COD removal in organic wastewater treatment process was improved from 75.6% to 86.6%, while the specific methane production by COD removal was increased by 2.7 times. Hydrogen-producing acetogenesis appeared to be a rate-limiting step in methane fermentation, and the enhancement of hydrogen-producing acetogens in the anaerobic wastewater treatment process had improved not only the hydrogen-producing acetogenesis but also the acidogenesis and methanogenesis.

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土壤渗滤法治理湿地水环境污染

根据扎龙自然保护区独特的地理、地质条件，研究采用土壤渗滤法处理排入湿地的造纸废水，并从技术和实践分析的角度对该地浅表部亚粘土渗滤的稳定性及可行性进行了探讨。结果表明：保护区地表层的亚粘土对造纸废水中各项污染物均有较好的去除效果，其CODCr、BOD5、Cr^6 、NH4^ -N及TP的去除率分别达到了70％、84％、90％、78％及80％以上，在该处利用缓坡土地渗滤处理系统是稳定可行的。     

Enhancement of As(V) adsorption onto activated sludge by methylation treatment

Biosorption properties of arsenate [As(V)] onto activated sludge were investigated in batch systems. The adsorption of As(V) onto sludge increased from 23 to 266 μg/g dry weight through the methylation of the activated sludge. This increase resulted from neutralization of carboxylic groups via the methylation process. The pH effect of As(V) uptake was also investigated and As(V) adsorption by methylated sludge decreased significantly at high pH (pH > 11) due to competition between As(V) and OH⁻ ions for binding sites distributed on sludge surfaces. In contrast, low pH favored As(V) adsorption by methylated sludge because of the elevated quantities of positively charged functional groups. The results suggest that methylated activated sludge may provide promising applications for the simultaneous removal and separation of As(V) from aqueous effluents.