3种苯胺类化学品在好氧污水处理模拟系统中的降解特性

采用好氧生化污水处理模拟实验方法,研究了不同水力停留时间(hydraulic retention time,HRT)下4-硝基苯胺、4-异丙基苯胺和2-氯-4-硝基苯胺的去除率.结果表明,HRT为6 h、12 h和24 h时,系统DOC去除率依次为70.2%、80.3%和88.3%,4-硝基苯胺去除率分别为48%、64.7%和75%,4-异丙基苯胺的去除率分别为66%、76%和91%,提高HRT可促进溶解性有机碳和苯胺类化学品的去除.2-氯-4-硝基苯胺在不同HRT条件下较难去除,去除率平均值低于20%.生物降解动力学实验结果表明,4-硝基苯胺、4-异丙基苯胺和2-氯-4-硝基苯胺在3 g·L~(-1)好氧活性污泥中的降解符合一级动力学方程,回归系数大于0.95,生物降解半衰期依次为6.01 h、16.16 h和123.75 h.异丙基对苯胺类化学品生物降解具有积极作用,而硝基和氯原子等基团抑制生物降解性.     

多壁碳纳米管对水中五氯苯酚的吸附性能研究

碳纳米管作为新型碳材料,具有独特的一维管状的微结构特性,使它具有优异的吸附性能,近几年受到研究者的高度重视。文章采用催化裂解法制备多壁碳纳米管,先经空气纯化,再以浓硝酸-浓硫酸氧化,将其用于处理水中难降解多氯代有机物-五氯苯酚。经透射电镜和比表面积分析表明,碳纳米管纯度高,孔隙均匀,内径为30nm左右,比表面积为150m2/g。考察碳纳米管对五氯苯酚的吸附性能和主要影响因素结果表明:碳纳米管对五氯苯酚吸附平衡时间为1h,是活性炭的1/10,吸附速率常数为0.0994min-1;吸附等温线符合Freundlich型;随着温度的升高,碳纳米管对五氯苯酚的吸附量减小;pH在4～10时随pH增加碳纳米管对五氯苯酚的吸附降低,pH大于10之后又上升,存在最低吸附量的pH值。     

4种典型抗生素在反硝化体系中的去除特性

污水处理厂是抗生素的重要汇集场所,反硝化是污水处理厂生物脱氮的关键环节.为了探究抗生素在反硝化污泥体系的去除特性,选取诺氟沙星(NOR)、土霉素(OTC)、磺胺甲■唑(SMX)和甲氧苄啶(TMP),对比研究了其在不同碳源条件下的变化规律,评估了吸附和生物降解等途径对抗生素去除的贡献.结果表明,反硝化脱氮体系对NOR、 OTC和TMP具有一定的去除作用,且NOR和OTC可被用作碳源进行反硝化.反硝化污泥对NOR和OTC的去除是快速吸附和缓慢生物降解的过程,其中,吸附对NOR和OTC总去除量的贡献率分别达到83.5%和58.9%,生物降解的贡献率分别为16.5%和41.1%.在吸附过程中,胞外聚合物(EPS)吸附的贡献率达到40%以上,而在OTC的生物降解过程中,P450酶发挥重要作用,其贡献率达到20%.     

巯基硅烷改性多壁碳纳米管的合成及其对Cd2+的吸附性能研究

利用3-巯丙基三甲氧基硅烷(MPTMS)作硅烷偶联剂对多壁碳纳米管(MWCNTs)进行改性,制备巯基硅烷改性多壁碳纳米管(SHMWCNTs),并进行了SH-MWCNTs对Cd~(2+)的批量吸附实验.同时,利用扫描电镜(SEM)、X射线光子能量仪(EDS)、红外光谱(FT-IR)对SHMWCNTs进行表征,探究了溶液初始pH、吸附剂投加量、吸附时间、溶液初始Cd~(2+)浓度等因素对吸附效果的影响,分析了吸附动力学特征及吸附等温线特征,初步探讨了吸附机理.SEM、EDS与FT-IR图谱显示,MPTMS已成功接枝到MWCNTs表面,表明SH-MWCNTs制备成功.吸附时间为90 min,pH为4时的吸附效果最佳,吸附量随SH-MWCNTs投加量、Cd~(2+)浓度的增加而增大.吸附动力学和吸附等温线研究表明,SHMWCNTs对Cd~(2+)的吸附动力学符合准二级线性方程,吸附等温线符合Freundlich、Langmuir 2种模型,吸附以单分子层吸附为主,也存在层间扩散的多层吸附.     

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.     

Adsorption of lead on multi-walled carbon nanotubes with different outer diameters and oxygen contents: Kinetics, isotherms and thermodynamics

The effects of different outer diameters and surface oxygen contents on the adsorption of heavy metals onto six types of multi-walled carbon nanotubes (MWCNTs) were investigated in an aqueous solution and lead was chosen as a model metal ion. The results indicated that the percentage removal and adsorption capacity of lead remarkably increased with decreasing outer diameter due to larger specific surface area (SSA). The SSA-normalized maximum adsorption capacity (qm /SSA) and SSA-normalized adsorption coefficient (Kd /SSA) were strongly positively correlated with surface oxygen content, implying that lead adsorption onto MWCNTs significantly increases with the rise of oxygen content and decreases with decreasing SSA. The calculated thermodynamic parameters indicated that adsorption of lead on MWCNTs was endothermic and spontaneous. When the oxygen content of MWCNTs increased from 2.0% to 5.9%, the standard free energy (△ G0 ) became more negative, which implied that the oxygenated functional groups increased the adsorption affinity of MWCNTs for lead. Through calculation of enthalpy (△ H0 ), G0 and free energy of adsorption (Ea ), lead adsorption onto MWCNTs was recognized as a chemisorption process. The chemical interaction between lead and the phenolic groups of MWCNTs could be one of the main adsorption mechanisms due to highly positive correlations between the phenolic groups and K d /SSA or q m /SSA.     

选择性生物强化处理二元互抑体系中苯胺和硝基苯

采用树脂吸附与生物强化相组合的方法处理含有苯胺和硝基苯的混合废水,对苯胺和硝基苯的降解抑制类型、吸附分离条件、生物强化降解过程与树脂性能变化等进行了研究.结果表明,硝基苯与苯胺均对对方的生物降解产生抑制;当进水中苯胺与硝基苯浓度分别为330与44mg/L时,在pH为4且流速为110mL/h条件下,通过装填有10mL吸附树脂NDA-150(7.2g)的吸附柱,吸附出水中硝基苯浓度低于4mg/L;吸附出水中苯胺的浓度保持不变,可通过生物强化而得到降解;吸附过程中约有597mg的硝基苯被树脂所吸附,其中约有224mg可通过生物强化方法得到脱附降解,系统降解硝基苯的容积负荷为315mg/(L·d);在此过程中树脂吸附能力获得部分恢复,其再生程度受到微生物对硝基苯降解能力的限制;70d的重复性实验证明,树脂性能保持稳定.     

Fenton改性多壁碳纳米管对亚甲基蓝的吸附性能研究

通过催化裂解法制备多壁碳纳米管,利用Fenton试剂对多壁碳纳米管改性,研究了Fenton改性对多壁碳纳米管表面物理化学特性的影响和对亚甲基蓝的吸附特性.投射电镜(TEM)、比表面积(BET)分析表明,Fenton改性多壁碳纳米管纯度高,孔隙均匀,外径为30nm左右,比表面积为120m2/g;且表面引入了大量含氧基团,等电点为1.8.未改性和Fenton改性多壁碳纳米管对亚甲基蓝的吸附动力学均符合Langergren模型,其平衡吸附量分别为24.5,36.4mg/g;吸附等温线均符合Freundlich模型,未改性和Fenton改性多壁碳纳米管的kF分别为7.92和25.37;温度和pH值升高均有利于Fenton改性多壁碳纳米管对亚甲基蓝的吸附.     

酸化时间对磁性碳纳米管制备及吸附菲的影响

采用共沉淀法对混酸氧化的多壁碳纳米管（MWCNTs）进行磁化,形成了Fe₃O₄/MWCNTs磁性复合材料（MMWCNTs）.研究了酸化时间对MMWCNTs制备及其吸附水中菲性能的影响.结果表明：弱酸条件下吸附效果较好,MMWCNTs对水中菲的吸附在30min内快速上升,到60min时基本达到平衡,吸附过程符合准二级动力学模型.MMWCNTs对水中菲的饱和吸附量随酸化时间增加呈现先升高后降低的趋势.酸化7h后制备的MMWCNTs的饱和吸附量最大,达到17.56μg/mg.     

好氧颗粒污泥及其高效菌株降解苯胺的试验研究

以苯胺为唯一碳源和氮源,培养降解高浓度苯胺废水的好氧颗粒污泥,该体系对苯胺废水的最高耐受浓度高达6 000mg/L.通过分离纯化,从颗粒污泥体系中获得2株具有不同降解特征的苯胺降解菌adx1和adx3,菌株adx1在降解速率上具有明显优势,而菌株adx3对苯胺的最高耐受浓度高于adx1.上述菌株在降解苯胺过程中均遵循Haldane动力学模型,菌株adx1和adx3的最大比较降解速率分别为0.924 g/(g.h)和0.645 g/(g.h),比生长速率分别为0.487 g/(g.h)和0.440 g/(g.h).16S rDNA测序结果表明adx1和adx3分别属于Pseudomonas和Achromobacter属,与好氧颗粒污泥PCR-DGGE指纹图条带1和4测序结果一致,表明上述菌株分别为好氧颗粒化体系中优势菌群之一.     

Solar photocatalytic decomposition of two azo dyes on multi-walled carbon nanotubes (MWCNTs)/TiO2 composites

Multi-walled carbon nanotubes (MWCNTs)/TiO₂ composite photocatalysts with high photoactivity were prepared by sol-gel process and further characterized by X-ray diffraction (XRD), scanning electron microscopy (SEM), Fourier transform infrared (FT-IR), and UV-vis absorption spectra. Compared to pure TiO₂, the combination of MWCNTs with titania could cause a significant absorption shift toward the visible region. The photocatalytic performances of the MWCNTs/TiO₂ composite catalysts were evaluated for the decomposition of Reactive light yellow K-6G (K-6G) and Mordant black 7 (MB 7) azo dyes solution under solar light irradiation. The results showed that the addition of MWCNTs enhanced the adsorption and photocatalytic activity of TiO₂ for the degradation of azo dyes K-6G and MB 7. The effect of MWCNTs content, catalyst dosage, pH, and initial dye concentration were examined as operational parameters. The kinetics of photocatalytic degradation of two dyes was found to follow a pseudo-first-order rate law. The photocatalyst was used for seven cycles with photocatalytic degradation efficiency still higher than 98%. A plausible mechanism is also proposed and discussed on the basis of experimental results.     

活性炭对苯胺、对硝基苯胺共吸附性能的研究

文章采用静态吸附法研究活性炭对苯胺和对硝基苯胺混合溶液中各组分的共吸附过程。研究结果表明,在吸附开始阶段,活性炭对各组分的吸附速率均较大,随着吸附时间的延长,其吸附速率减慢。活性炭对两组分吸附的动力学行为均遵循Bangham速率方程,且由于苯胺的分子极性较小,活性炭对苯胺的吸附速率比对硝基苯胺对大。对于不同浓度比的混合溶液,吸附质浓度越大,活性炭对其吸附量越大。混合溶液中对硝基苯胺的浓度越大,活性炭的总吸附速率和吸附量越大。当pH值为4～5时活性炭对苯胺的吸附性能优,而pH值对活性炭对对硝基苯胺的吸附量影响较小。活性炭对两组分的吸附量和吸附速率都随着温度的升高而增加,说明吸附反应为吸热反应。活性炭对苯胺的吸附反应活化能为24.21kJ/mol,对对硝基苯胺的吸附反应活化能为54.98kJ/mol,温度升高更有利于活性炭对对硝基苯胺的吸附。     

生物活性炭投加量对垃圾渗滤液处理效果的影响

试验对比了不同生物活性炭(biological activated carbon,BAC)投加量对垃圾渗滤液去除COD效果的影响.每升活性污泥中活性炭投加量为0、100、300 g的反应器处理垃圾渗滤液100个周期平均COD去除率分别为12.9%、19.6%、27.7%,表明BAC可以去除部分难降解有机物,并且COD去除率与投加量呈正相关关系.曝气8 h反应器中二氧化碳(CO2)产生量依次为109、193、306 mg,表明生物分解量也与投加量呈正相关关系.分析认为COD去除率与投加量的正相关关系是由于吸附与生物再生的共同作用导致,生物再生是BAC能够生物分解难降解有机物的根本原因.     

多壁碳纳米管长期作用对活性污泥系统的影响

为研究MWCNTs(multi-walled carbon nanotubes,多壁碳纳米管)对活性污泥长期作用的影响,建立3组(每组包括3个平行反应器)序批式活性污泥反应器,研究了2种质量浓度(1、20 mg/L)的MWCNTs长期(120 d)作用对活性污泥系统废水处理效果的影响,并采用Illumina MiSeq高通量测序技术研究MWCNTs长期作用后活性污泥中细菌群落结构的变化. 结果表明:20 mg/L的MWCNTs对生物脱氮效果存在明显的抑制作用,TN平均去除率由83.4%降至71.7%;1 mg/L的MWCNTs长期作用后TN平均去除率由83.7%降至79.7%. 1和20 mg/L的MWCNTs对磷的去除均有抑制作用,TP平均去除率分别由98.0%和98.2%降至52.0%和34.0%. Illumina MiSeq高通量测序结果表明,不同质量浓度的MWCNTs长期作用后降低了活性污泥中细菌群落的多样性. 同时,活性污泥中细菌群落结构也发生了变化,其中α-Proteobacteria和γ-Proteobacteria的丰度升高,Bacteroidetes的丰度降低. 1 mg/L的MWCNTs长期作用可致以Defluviicoccus和Micropruina为代表的一类聚糖菌(glycogen-accumulating organisms, GAOs)丰度显著升高,20 mg/L的MWCNTs长期作用可致16个核心属的丰度明显降低.      

Phosphine functionalised multiwalled carbon nanotubes: A new adsorbent for the removal of nickel from aqueous solution

Synthesised triphenylphosphine-linked multiwalled carbon nanotubes (Tpp-MWCNTs) were used to study the adsorption of nickel in aqueous solutions and their adsorption capabilities were compared with purified MWCNTs. The adsorption capacity increased with an increase in pH for all adsorbents. The adsorption equilibrium was reached in 40 and 30 min for purified MWCNTs and Tpp-MWCNTs, respectively. Both Freundlich and Langmuir isotherms used to investigate the adsorption process fitted the experimental data well with the correlation coefficient R² close to 1 for all adsorbents. On the other hand, the experimental data fitted well with a pseudo second-order model. The speciation of nickel also influenced the adsorption on the purified and Tpp-MWCNTs. The adsorbents used in this study showed superior adsorption capacity when compared to other adsorbents reported in the literature.     

氨基化碳纳米管/石墨烯气凝胶对甲醛吸附研究

针对目前室内空气污染物甲醛超标的现象,将新型碳纳米材料(石墨烯、碳纳米管)引入到气体污染物去除领域.利用石墨烯水溶液在一定条件下形成凝胶的特性,采用海绵作为骨架,构造石墨烯/碳纳米管/海绵三维气凝胶结构,并进一步采用氨基修饰提高该氨基化碳纳米管/石墨烯气凝胶(GCNTs/EDA-S)对室内空气污染物甲醛的吸附性能,研究石墨烯与碳纳米管(CNTs)对气态甲醛吸附作用机理.样品吸附实验结果对比分析表明,石墨烯和碳纳米管氨基官能团修饰后对气态甲醛均有良好的吸附性能,其中GCNTs/EDA-S在甲醛浓度为3.7ppm时,吸附实验的穿透时间可达到4024min/g,最大吸附容量为13.5mg/g.     

MWCNTs预涂覆及预吸附处理缓解低压膜腐殖酸污染的机制研究

以腐殖酸(Humic Acid,HA)为研究对象,采用多壁碳纳米管(Multiwalled Carbon Nanotubes,MWCNTs)对聚偏氟乙烯(Polyvinylidene Fluoride,PVDF)平板超滤膜进行预涂覆改性处理,并与等量MWCNTs分散状态时吸附处理HA对膜污染的缓解效果进行了对比,考察了MWCNTs在处理HA过程中缓解膜污染的机制.同时,分析了MWCNTs投量和溶液离子变化对MWCNTs吸附及截留作用缓解膜污染的影响.结果表明,MWCNTs预涂覆与吸附相比,能够更有效地缓解膜污染,其中,分散剂为乙醇的MWCNTs预涂覆层对膜污染的缓解效果最好.增加MWCNTs投量不能无限地提高其对HA的吸附及截留效果;添加Na~+会造成MWCNTs对HA的吸附及截留效果变差;添加Ca~(2+)能够提高MWCNTs对HA的吸附及截留效果.膜表面污染照片及膜电镜观测结果表明,乙醇分散MWCNTs在超滤膜(UF)表面形成的预涂覆层呈均匀的层状结构,HA被拦截在MWCNTs层的多孔结构内,不易进入PVDF膜膜孔,反洗时易脱附,可逆性高;纯水分散MWCNTs在超滤膜表面形成的预涂覆层易于团聚,HA容易透过MWCNTs涂覆层进而堵塞PVDF膜膜孔,可逆性低;MWCNTs预吸附处理后形成MWCNTs和HA的包裹体,不经微滤膜滤除,会在PVDF膜表面产生复合污染.     

生物炭降解苯和甲苯混合废气性能研究

该研究以生物炭为过滤介质 ,探讨过滤塔降解气流中苯、甲苯的生物降解性能 .实验表明 ,在总有机负荷低于 3 5 0 g/ (h·m3)、停留时间 1 5～ 90s的实验条件下 ,滤塔对苯和甲苯混合气体有较好的降解性能 ,苯、甲苯的最大削减能力分别为 1 2 0 g/ (h·m3)和 1 5 0 g/ (h·m3) ,甲苯比苯更易被微生物降解 .滤塔中CO2 生成量随苯、甲苯降解量的增加而增加 ,但实验增长速率小于理论增长速率 .菌落分析表明 ,滤塔中微生物主要有真菌、杆菌、芽孢杆菌 ,其中芽孢杆菌为优势菌种 .根据吸附 生物降解机理 ,建立了VOCs去除模型 ,并予以验证 .     

碳质纳米材料与枝孢菌KR14的相互影响研究

碳质纳米材料(Carbon Nanomaterials, CNMs)因具有独特的电学及光学等性质而引起了人们的广泛关注,从而被大量使用并释放到环境中,进而影响生态系统环境及生物化学过程,但目前有关CNMs与环境微生物相互作用的研究鲜见报道.因此,本文研究了枝孢菌KR14(Cladosporium sp.)与3种CNMs(单壁碳纳米管(SWCNTs)、石墨烯(Graphene)和氧化石墨烯(GO))的相互作用.结果表明,CNMs的加入促进了3种非特异性酶(漆酶、锰过氧化物酶和木质素过氧化物酶)活性增加,其中,对锰过氧化物酶(MnP)活性的促进作用最为显著,18 d最高增加26.1%.在3种类型的CNMs中,SWCNTs对MnP活性刺激最佳,GO最弱.木质素降解实验和电化学分析表明,CNMs可作为电子导体提高真菌胞外电子传递效率,进而提高KR14对木质素的降解.X射线光电子能谱(XPS)结果表明,除GO外,SWCNTs和石墨烯的氧碳比(O/C)均上升,二者表面发生变化.拉曼光谱(Raman)和傅立叶变换红外光谱(FTIR)结果表明,SWCNTs的I_D/I_G显著提高,无序性增加;石墨烯出现2D峰,即与KR14相互作用后有一定程度堆叠;KR14可引起CNMs结构转变.本研究结果有助于深入理解和评价环境中CNMs与真菌之间的相互作用关系及CNMs对真菌降解木质素和环境碳循环的影响.