MOFs/水凝胶复合材料的制备及其应用研究

金属有机框架(MOFs)具有大量的孔隙结构和活性位点,在气体吸附、催化、医疗等领域均发挥了巨大的作用。MOFs是晶体粉末,具有脆性较大、在水中易分解和不易回收等缺点,从而限制了其应用。通过MOFs与柔性高分子的复合,特别是与水凝胶的复合,极大地改善了复合材料的柔顺性、可回收和可加工性等特性,进一步拓宽了MOFs的应用领域。本文详细阐述了基于水凝胶MOFs原位生成法、MOFs /水凝胶同时生成法和水凝胶包裹MOFs法等三种不同方法制备MOFs/水凝胶复合材料的研究进展,并对上述三种制备方法的特点及其产物特征进行了总结,进一步归纳了复合材料在生物医药、催化、废水处理和气体吸附等领域的应用。最后,对MOFs/水凝胶复合材料制备方法的改进和复合材料应用前景进行了深入讨论和展望。     

Sequential separation of Cu(II)/Ni(II)/Fe(II) from strong-acidic pickling wastewater with a two-stage process based on a bi-pyridine chelating resin

A self-synthesized bi-pyridine chelating resin (PAPY) could separate Cu(II)/Ni(II)/Fe(II) sequentially from strong-acidic pickling wastewater by a two-stage pH-adjusted process, in which Cu(II), Ni(II), and Fe(II) were successively preferred by PAPY. In the first stage (pH 1.0), the separation factor of Cu(II) over Ni(II) reached 61.43 in Cu(II)-Ni(II)-Fe(II) systems. In the second stage (pH 2.0), the separation factor of Ni(II) over Fe(II) reached 92.82 in Ni(II)-Fe(II) systems. Emphasis was placed on the selective separation of Cu(II) and Ni(II) in the first-stage. The adsorption amounts of Cu(II) onto PAPY were 1.2 mmol/g in the first stage, while those of Ni(II) and Fe(II) were lower than 0.3 mmol/g. Cu(II) adsorption was hardly affected by Ni(II) with the presence of dense Fe(II), but Cu(II) inhibited Ni(II) adsorption strongly. Part of preloaded Ni(II) could be replaced by Cu(II) based on the replacement effect. Compared with the absence of Fe(II), dense Fe(II) could obviously enhance the separation of Cu(II)-Ni(II). More than 95.0% of Cu(II) could be removed in the former 240 BV (BV for bed volume of the adsorbent) in the fixed-bed adsorption column process with the flow rate of 2.5 BV/h. As proved by X-ray photoelectron spectrometry (XPS) and density functional theory (DFT) analyses, Cu(II) exerted a much stronger deprotonation and chelation ability toward PAPY than Ni(II) and Fe(II). Thus, the work shows a great potential in the separation and purification of heavy metal resources from strong-acidic pickling wastewaters.     

列车集便系统使用现状及污水资源化新思路

调研了旅客列车集便系统使用情况及排污处理现状,发现由于经济、技术、人为等问题,列车密闭式厕所短期内推广存在困难,集便器污水地面接收方式过于单一,并且处理系统不健全,不合理。分析了传统资源化方法处理列车集便器污水的局限性;提出了使用粪尿分离式集便系统实现源头控制的方法,这种粪尿源头分离的方法大大降低了处理难度,同时可以带来很好的经济效益和社会效益。     

电催化氧化处理垃圾渗滤液

以复极性固定床电解槽为反应器,利用CuO-CeO₂/γ-Al₂O₃多相催化剂取代传统反应器的绝缘填料,构建电催化氧化体系。采用XRD、SEM对CuO-CeO₂/γ-Al₂O₃进行表征,考察了槽电压、pH、气体流量和极间距等因素对垃圾渗滤液降解的影响。结果表明,该体系对渗滤液具有较好的催化降解效果。当槽电压为15.0V、pH为中性、气体流量为0.08m³/h、极间距为3.0cm时,垃圾渗滤液COD和NH⁺₄-N的去除率分别达到93.7%和100%。在处理垃圾渗滤液的过程中,体系运行稳定,经过20次反复实验,降解效果仍能维持在70%以上。在电催化氧化体系的作用下,垃圾渗滤液中的难降解有机污染物被直接矿化或降解为小分子有机物;而NH⁺₄-N则主要被氧化为氮气和水。     

粘红酵母处理味精废水的研究

对粘红酵母处理味精废水的条件进行研究。结果表明最佳处理条件为：进水COD浓度为10000mg/L,pH为6.16,发酵温度为32℃,发酵时间为72h,接种量为15%。该条件下可使味精废水COD的去除率达80.53%以上,利用发酵后的菌体,可提取单细胞蛋白,提取油脂,具有一定的应用潜力。     

生物滤池废水处理过程数学模型的求解和验证

利用基于定层数、定密度和变层厚的差分解法,求解多组分、多物种生物滤池模型（CM—MDMB）,并用试验实例检验了模型（CMMDMB）对生物滤池内生物膜厚度和微生物组分结构以及滤池处理的模拟效果．检验的结果表明,模型（CMMDMB）能有效地模拟生物滤池的运行效果．     

Abatement of cyanide and ammoniacal-N from coke-oven wastewater using natural adsorbents: A comparative study

The present study aims at efficient abatement of pollutants from coke-oven wastewater using environment-friendly and low-cost adsorbents for a green world. The adsorbent used were native laterite soil (NLS), heat-treated laterite soil (HTLS), native shale (NS) and Heat-treated shale (HTS). One factor at a time (OFAT) approach was followed to determine the most effective condition based on the maximum removal. Heat-treated laterite soil and native shale were found most effective among their counterparts. Freundlich model was found best to analyze equilibrium data. The real coke-oven wastewater was collected and experiments were performed in batch mode. The percentage removal of cyanide (88.09% and 95.31%) and ammoniacal-N (87.28% and 92.12%) were found satisfactory when heat-treated laterite soil and native shale were used as adsorbents, respectively.     

湿式氧化用于染料废水脱色:过去20年回顾（英文）

Wet air oxidation(WAO), a liquid phase reaction between organic materials in water and oxygen, is one of the most economical and technologically viable advanced oxidation processes for wastewater treatment, particularly toxic and high organic content wastewater. WAO is the liquid phase oxidation of organics or oxidizable inorganic components at elevated temperatures(125–320 °C) and pressures(0.5–20 MPa) using gaseous oxygen(or air) as oxidant. In the past two decades, the WAO process was widely studied and applied in the treatment of dye wastewater. Compared to conventional WAO, catalytic WAO processes have higher efficiency and use moderate reaction conditions. The catalysts included homogenous and heterogeneous types. The key points that need to be solved are recycling of homogenous catalysts and better stability of heterogeneous catalysts. In the present review, the technological processes are first introduced, then some research history and hotspots of WAO research are presented, and finally, its application in the treatment of dye wastewater in the past two decades is summarized to reveal the impressive changes in modes, trends, and conditions used. The application includes model pollutant studies and wastewater tests.     

悬浮固化-分散液液微萃取-液相色谱-串联质谱测定纺织废水中磷系阻燃剂

建立了悬浮固化-分散液液微萃取结合液相色谱-串联质谱测定纺织废水中5种痕量磷系阻燃剂的方法。通过对萃取过程中萃取剂、分散剂的种类与体积、盐浓度、溶液pH值等对萃取效率的影响因素优化,确立了最佳萃取条件。采用了密度小于水的十一烷醇（400 μL）为萃取剂,甲醇（300 μL）为分散剂,控制溶液pH值在6~9之间,NaCl添加量为2 g,萃取时间为涡旋2 min。在优化的萃取条件下,该方法在2~100 μg/L均有良好的线性关系,相关系数大于0.995,除二（2,3-二溴丙基）磷酸酯（BIS）的检出限为5 μg/L外,三（2-氯乙基）磷酸酯（TCEP）、三（1,3-二氯-异丙基）磷酸酯（TDCP）、三（1-氮丙啶基）氧化膦（TEPA）和三（2,3-二溴丙基）磷酸酯（TRIS）的检出限均为2 μg/L。后整理、染色和印花等实际废水样品加标试验表明,方法的平均回收率为71.6%~114.5%,RSD为2.7%~11.2%（n=6）。对11个样品进行检测,其中3个废水样品检出TCEP与TDCP化合物,含量为2.6~3.4 μg/L。本方法简单,快速,灵敏度好且环保绿色,能够对纺织废水中的5种痕量磷系阻燃剂进行准确的定性与定量检测。     

高氯废水化学需氧量分析方法综述

对高氯废水化学需氧量分析方法进行归纳和综述。常用的高氯废水化学需氧量分析方法有氯气校正容量法、降氯密闭消解分光光度法以及高温氧化总有机碳系数换算法等。其中氯气校正容量法操控要求较高,分析耗时较长,不适用于大批量样品同步分析;降氯密闭消解分光光度法灵敏度高,但在降氯过程中增加了重金属盐硫酸汞的用量,分析成本较高,易产生二次污染,且对样品的均质性要求较高;高温氧化总有机碳系数换算法操作便捷、抗干扰能力强,但是换算系数易随不同来源、不同组分的样品发生波动,数据可比性需要通过实验验证。经过梳理归纳,明确各种分析方法的特点和适用范围,为研究人员选择合适的分析方法或进一步开展相关的方法研究提供参考。