催化剂Ru/ZrO2-CeO2催化湿式氧化苯酚

催化剂Ru/ZrO₂-CeO₂催化湿式氧化苯酚的过程表明,Ru/ZrO₂-CeO₂可以显著提高COD和苯酚去除效果,当反应温度为170℃,压力为3 MPa,反应120 min后,COD和苯酚的去除率分别达到了99％和100％.试验还考察了不同反应条件对苯酚溶液COD去除的影响,并获得了最优的反应条件：温度为170℃,压力为3 MPa,催化剂的投加量为5　g/Ｌ,搅拌速度为500 r/min.通过对中间产物的分析,本研究提出了催化湿式氧化苯酚的简单路径图,认为苯酚首先被氧化成小分子有机酸,接着小分子有机酸被氧化成二氧化碳和水.前一个过程是快速反应,后一个过程中的乙酸氧化是慢速过程,需要在高温下才能完成.乙酸的氧化主要是自由基攻击α碳上的C—H键,先生成甲酸,并最终生成二氧化碳和水.     

Biodegradation of phenol by free and immobilized Acinetobacter sp. strain PD12

A new phenol-degrading bacterium with high biodegradation activity and high tolerance of phenol, strain PD 12, was isolated from the activated sludge of Tianjin Jizhuangzi Wastewater Treatment Facility in China. This strain was capable of removing 500 mg phenol/L in liquid minimal medium by 99.6% within 9 h and metabolizing phenol at concentrations up to 1100 mg/L. DNA sequencing and homologous analysis of 16S rRNA gene identified PD12 to be an Acinetobacter sp. Polyvinyl alcohol （PVA） was used as a gel matrix to immobilize Acinetobacter sp. strain PDI2 by repeated freezing and thawing. The factors affecting phenol degradation of immobilized cells were investigated, and the results showed that the immobilized cells could tolerate a high phenol level and protected the bacteria against changes in temperature and pH. Storage stability and reusability tests revealed that the phenol degradation functions of immobilized cells were stable after reuse for 50 times or storing at 4℃ for 50 d. These results indicate that immobilized Acinetobacter sp. strain PD 12 possesses a good application potential in the treatment of phenol-containing wastewater.     

Pd/C气体扩散电极用于电生成H2O2降解苯酚的研究

采用自制的Pd/C气体扩散阴极和Ti/IrO2/RuO2阳极,在无隔膜电解槽中对苯酚模拟废水降解效果及机制进行了研究,采用电子自旋共振法(ESR)对电解体系中产生的羟自由基(·OH)进行了检测.结果表明,在Pd/C气体扩散体系中掺杂Pd催化剂可以促进H2 O2的生成(H2 O2的稳定浓度是7.5 mg/L),有利于·OH的产生.经电化学氧化处理120 min后,苯酚和COD的去除率分别达到97.2%和50%,表明在电催化氧化过程中苯酚被氧化生成了大量低分子量中间产物.废水的BOD5/COD值达到0.73是处理前的9.1倍,苯酚废水的可生化降解性通过电化学氧化处理后显著提高.在该电化学体系中苯酚的降解是在阳极直接、间接氧化及阴极产生的H2 O2、·OH的氧化共同作用下完成的.通过对紫外扫描光谱图的分析推断出苯酚在电解过程中有醌类物质生成;由GC-MS检测到了邻苯二酚、对苯二酚、苯醌等芳香族化合物和己二酸、顺丁烯二酸、反丁烯二酸、丁二酸、丙二酸、乙二酸等短链羧酸,据此提出了苯酚降解的可能历程.     

Roles of manganese oxides in degradation of phenol under UV-Vis irradiation: Adsorption, oxidation, and photocatalysis

The effect of crystal structure on photocatalytic activities of manganese oxides and underlying reaction mechanism were investigated.     

挥发回转窑处置钢丝绳行业污泥的污染物排放研究

通过利用挥发回转窑处置钢丝绳行业污泥的工业化试验,测定了烟气排放参数及污染物排放指标,分析了污泥添加对挥发回转窑烟气排放的影响程度及各项污染物指标之间的相关性。结果表明,污泥添加量18%～22%,对挥发回转窑烟气排放无影响,烟尘、SO2、氮氧化物、Zn、Pb、HCl等各项污染物指标均符合国家控制标准;烟尘排放浓度与Pb、Zn排放浓度呈显著正相关;SO2排放浓度与烟气含氧量、空气过剩系数、排放浓度呈显著负相关。通过控制烟气中烟尘浓度可减少Zn、Pb的排放,在满足SO2排放浓度达标的同时,还应加强工艺供氧量的管理,控制的产生,减少烟气对生产设备的腐蚀。     

苯酚对活性污泥活性及微型动物群落结构的影响

为了探究苯酚对污泥活性及微型动物群落结构的影响,以SBR工艺的活性污泥为研究对象,分析苯酚对污泥TTC-ETS活性、INT-ETS活性和微型动物群落结构及其动态变化的影响.结果表明,污泥TTC-ETS活性较之INT-ETS活性能够更有效表征有机毒害物质苯酚对污泥活性的影响,且随着进水苯酚浓度的增大,苯酚对污泥活性的抑制越明显:进水浓度在50mg·L-1时,苯酚对污泥活性的抑制率为(20.75±10.43)%.进水苯酚浓度为100 mg·L-1时,抑制率为(39.73±26.92)%,且波动较大.在300 mg·L-1进水运行后期,苯酚对污泥活性的抑制率稳定在40%左右;苯酚对活性污泥微型动物群落结构的影响随浓度的增大而增大,且对不同微型动物类群影响不同:在低浓度苯酚进水条件下,只有单个微型动物类群(有壳变形虫)受到明显的抑制,而当浓度增大至100 mg·L-1和300 mg·L-1时,对多个微型动物类群(固着型纤毛虫、有壳变形虫、匍匐型纤毛虫、肉食性纤毛虫等)产生抑制,对少数类群(鞭毛虫、线虫等)产生促进作用;苯酚影响下的污泥活性与微型动物之间存在一定的关联性,针棘匣壳虫(Centropyxis aculeata)、多变斜板虫(Plagiocampa mutabilis)等可作为含酚废水处理过程中污泥活性低的指示生物,湖累枝虫(Epistylis lacustris)、软波豆虫(Bodo lens)、跳侧滴虫(Pleuromonas jaculans)等可作为污泥活性高的指示生物.     

Reaction mechanism and metal ion transformation in photocatalytic ozonation of phenol and oxalic acid with Ag+/TiO2

Photocatalytic ozonation of phenol and oxalic acid （OA） was conducted with a Ag^＋/TiO2 catalyst and different pathways were found for the degradation of different compounds. Ag^＋ greatly promoted the photocatalytic degradation of contaminants due to its role as an electron scavenger. It also accelerated the removal rate of OA in ozonation and the simultaneous process for its complex reaction with oxalate. Phenol could be degraded both in direct ozonation and photolysis, but the TOC removal rates were much higher in the simultaneous processes due to the oxidation of hydroxyl radicals resulting from synergetic effects. The sequence of photo-illumination and ozone exposure in the combined process showed quite different effects in phenol degradation and TOC removal. The synergetic effects in different combined processes were found to be highly related to the properties of the target pollutants. The color change of the solution and TEM result confirmed that Ag＋ was easily reduced and deposited on the surface of Tit2 under photo-illumination, and dissolved again into solution in the presence of ozone. This simple cycle of enrichment and distribution of Ag^＋ can greatly benefit the design of advanced oxidation processes, in which the sequences of ozone and photo-illumination can be varied according to the needs for catalyst recycling and the different properties of pollutants.     

苯酚微生物降解的正交实验研究

利用以苯酚为碳源的驯化液,对某焦化厂曝气池活性污泥进行驯化,经过分离、筛选,挑选出4株高效的苯酚降解菌,编号为h32a2、b31B、h31A和b41a,并通过菌落形态特征、简单染色及生理生化反应初步鉴定为假单胞菌属(Pseudomonas sp.),依据正交实验确定了优势菌群降解苯酚的最佳条件为温度32℃,pH值7.5,菌培养时间16 h,接种量1%。     

Ce3+与Cu2+协同强化芬顿体系氧化苯酚的效能与机制研究

研究了Ce~(3+)与Cu~(2+)协同强化芬顿体系在不同初始条件下对水中苯酚的氧化效能与机制.结果表明,在p H适用范围的宽度和H_2O_2浓度变化方面,Ce~(3+)/Cu~(2+)/Fe~(2+)/H_2O_2体系比传统的芬顿体系更具有优势,该体系在p H=5.0、H_2O_2浓度为2.0mmol·L-1的条件下,仍可以对苯酚保持相对较高的氧化效能;Cu~(2+)可能会借助反应过程中的中间产物(醌类物质)生成Cu+,Cu+催化H_2O_2分解生成·OH,Ce~(3+)可能促进体系内醌类物质的形成,加快Fe~(3+)与Fe~(2+)的循环效能,在一定程度上提高了芬顿体系中H_2O_2分解生成·OH的速率,说明Cu~(2+)与Ce~(3+)对芬顿体系的强化作用具有协同性;自由基终止剂依然可以抑制Ce~(3+)、Cu~(2+)强化的芬顿体系对苯酚的降解,由此说明体系中起到氧化作用的活性物种仍然是羟基自由基(·OH).     

苯酚、菲在BS-12/DTAB复配修饰膨润土上吸附的差异

为了探究复配修饰膨润土吸附疏水性不同的污染物的差异,采用阳离子型表面修饰剂十二烷基三甲基溴化铵(DTAB)对两性表面修饰剂十二烷基二甲基甜菜碱(BS-12)修饰膨润土进行复配修饰,采用批处理法研究复配修饰膨润土总修饰比例对苯酚和菲的等温吸附影响,并对比不同温度、pH值和离子强度条件下供试土样对苯酚和菲吸附量、热力学参数的差异.结果表明:随着总修饰比例的增大,复配修饰膨润土对苯酚及菲的吸附能力逐渐增强,0~50%CEC修饰比例下,菲的吸附率大于苯酚的吸附率,当修饰比例超出50%CEC后,苯酚的吸附率大于菲的吸附率,总修饰比例超出150%CEC后,膨润土对苯酚的吸附率变化趋于平缓,而对菲的吸附率开始呈下降趋势;随着土样总修饰比例的增大,温度对苯酚及菲吸附量的抑制效果降低;在KNO_3浓度为0.001~0.1 mol·L~(-1)时,苯酚及菲的吸附量均随着KNO_3浓度的增大而增大;随着pH值的升高,苯酚的吸附量逐渐增大,在pH=7处达到最大,而菲的吸附量则始终呈降低趋势.热力学参数显示,随着总修饰比例的增大,复配修饰土样对苯酚和菲的吸附自发性增强,混乱度增大,当总修饰比例超出150%CEC后,自发性减弱,混乱度下降.