TiO2纳米管催化活性再生处理技术

采用H2O2、Fe2（SO4）3和Fenton溶液对失活的TiO2纳米管进行再生处理,重点考察了3种溶液的浓度和处理时间等对再生效果的影响,初步分析了经处理后TiO2纳米管催化活性得到再生或增强的机理。结果表明,经H2O2溶液处理后TiO2催化活性能得到有效再生,经Fe2（SO4）3,和Fenton溶液处理后其催化活性不仅得到再生,还能显著增强,这与H2O2和Fenton的强氧化作用,及进入TiO2纳米管的Fe3＋的阻止电子．空穴对再复合作用有关。     

Catalytic reductive dechlorination of p–chlorophenol in water using Ni/Fe nanoscale particles

Nanoscale bimetallic Ni/Fe particles were synthesized from the reaction of sodium borohydride （NaBH4） with reduction of Ni^2＋ and Fe^2＋ in aqueous solution. The obtained Ni/Fe particles were characterized by TEM （transmission electron microscope）, XRD （X-ray diffractometer）, and N2-BET. The dechlorination activity of the Ni/Fe was investigated using p-chlorophenol （p-CP） as a probe agent. Results demonstrated that the nanoscale Ni/Fe could effectively dechlorinate p-CP at relatively low metal to solution ratio of 0.4 g/L （Ni 5 wt%）. The target with initial concentration ofp-CP 0.625 mmol/L was dechlorinted completely in 60 rain under ambient temperature and pressure. Factors affecting dechlorination efficiency, including reaction temperature, pH, Ni loading percentage over Fe, and metal to solution ratio, were investigated. The possible mechanism of dechlorination ofp-CP was proposed and discussed. The pseudo-first- order reaction took place on the surface of the Ni/Fe bimetallic particles, and the activation energy of the dechlorination reaction was determined to be 21.2 kJ/mol at the temperature rang of 287-313 K.     

Metabolism of benzo[a]pyrene in peroxynitrite/Fe(Ⅲ) porphyrin system

The peroxynitrite/porphyrin biomimetic system was established to investigate the effects of peroxynitrite on benzo[a]pyrene (B[a]P) metabolism. Through the comparison of three model systems consisting of different iron porphyrins, we found that the peroxynitrite/T(p-Cl)PPFeCl system showed the highest catalytic efficiency in the metabolism of B[a]P. We analyzed the B[a]P metabolites produced from this system by RP-HPLC method and firstly identified the formation of nitrobenzo[a]pyrenes which are the special metabolites of B[a]P induced by peroxynitrite.     

Degradation of carbamazepine by MWCNTs-promoted generation of high-valent iron-oxo species in a mild system with O-bridged iron perfluorophthalocyanine dimers

Metal phthalocyanine has been extensively studied as a catalyst for degradation of carbamazepine (CBZ). However, metal phthalocyanine tends to undergo their own dimerization or polymerization, thereby reducing their activity points and affecting their catalytic properties. In this study, a catalytic system consisting of O-bridged iron perfluorophthalocyanine dimers (FePcF₁₆-O-FePcF₁₆), multi-walled carbon nanotubes (MWCNTs) and H₂O₂ was proposed. The results showed MWCNTs loaded with FePcF₁₆-O-FePcF₁₆ can achieve excellent degradation of CBZ with smaller dosages of FePcF₁₆-O-FePcF₁₆ and H₂O₂, and milder reaction temperatures. In addition, the results of experiments revealed the reaction mechanism of non-hydroxyl radicals. The highly oxidized high-valent iron-oxo (Fe(IV)=O) species was the main reactive species in the FePcF₁₆-O-FePcF₁₆/MWCNTs/H₂O₂ system. It is noteworthy that MWCNTs can improve the dispersion of FePcF₁₆-O-FePcF₁₆, contributing to the production of highly oxidized Fe(IV)=O. Then, the pathway of CBZ oxidative degradation was speculated, and the study results also provide new ideas for metal phthalocyanine-loaded carbon materials to degrade emerging pollutants.     

废聚苯乙烯塑料热降解回收苯乙烯单体的研究

为了废弃物资源化利用,建立了废聚苯乙烯热降解的实验室装置,探讨了影响聚苯乙烯热降解的因素,如温度,压力,催化剂用量等,在优化条件下获得９７．６％的分解油,其中苯乙烯单体含量达５５．５％,对聚苯乙烯热降解的机理进行了初步探讨,并预测了在工业化放大情况下该工艺的经济效益。     

半焦负载钙和铁催化还原NO的研究

用浸渍法制备负载Ca和Fe的褐煤半焦,采用程序升温和恒温法在石英固定床反应器上于常压反应条件下研究了NO-半焦催化还原反应.研究发现,Ca和Fe对半焦还原NO的反应具有催化作用,其中Fe的催化作用强于Ca;热处理温度升高,Ca的催化作用降低,但热处理温度的变化基本不影响Fe的催化活性;CO和O₂气氛可以促进NO的还原,温度升高CO和O₂的促进作用减小.     

V-W/TiO_2/γ-Al_2O_3催化剂催化还原NO的研究

掺杂15%TiO2对γ-Al2O3改性制备了TiO2/γ-Al2O3复合氧化物载体,以此复合氧化物及TiO2、γ-Al2O3为载体用浸渍法负载钒钨制备了一系列催化剂,采用比表面积和孔结构分析、X射线衍射(XRD)、高分辨电镜(HRTEM)、原位红外(in situ FT-IR)等技术对载体和催化剂进行宏观-微观表征,同时在模拟氨气选择性催化还原NO(NH3-SCR)的反应条件下对催化剂的脱硝反应活性进行考察,比较研究TiO2掺杂对V2O5-WO3/TiO2和V2O5-WO3/γ-Al2O3催化剂的改性作用。结果发现,少量TiO2掺杂制得的TiO2/γ-Al2O3复合载体中,TiO2和γ-Al2O3之间的协同作用使得V2O5-WO3/TiO2/γ-Al2O3催化剂的选择性催化还原脱硝效率及活性窗口明显优于单一载体制备的催化剂,并表现出了良好的热稳定性;各种表征结果表明,TiO2/γ-Al2O3复合载体中TiO2高度分散在γ-Al2O3上,复合载体具有较大的比表面积,载体表面存在大量的Br?nsted酸位和较多的活性中间产物,这些可能是TiO2/γ-Al2O3复合载体催化剂具有较好SCR活性的原因。     

微波加热下苯的催化氧化性能研究

研究考察了微波加热与传统电炉加热两种不同加热方式下苯的催化氧化性能,同时考察了微波加热下铜锰质量比,铈掺杂量及焙烧温度变化对铜-锰-铈/分子筛催化剂催化氧化苯性能的影响,并对催化剂进行了SEM和XRD表征.结果表明,微波加热下苯的催化氧化性能优于电炉加热,微波的"局部热点"效应、偶极极化作用与稳定的床层反应温度保证了苯的高效催化氧化;铜∶锰∶铈质量比1∶1∶0.33和焙烧温度500℃下催化剂的活性最高,苯的起燃温度与完全燃烧温度分别为165℃和230℃.催化剂表征分析可知,铜、锰氧化物及铜锰尖晶石固溶物等活性相的存在保证了催化剂的高活性;稀土元素铈的掺杂促进了活性组分在催化剂表面的分散与规整化;高温焙烧可导致催化剂表面的烧结与活性组分的团聚,从而降低其催化氧化苯的活性.     

Pd/Fe0双金属复合催化纤维降解水中痕量亚硝基二甲胺

存在于环境水体中的亚硝基二甲胺(NDMA)是一种强致癌性有机物,采用零价铁催化还原技术可以将其降解转化为低毒性物质,针对水中痕量NDMA的去除,需要深入开展基于高效零价铁材料、还原性能及还原机制方面的研究.以聚丙烯(PP)纤维为基材,采用紫外辐射接枝-金属离子配位-化学还原方法制备了含Pd/Fe~0双金属的复合催化纤维(Pd/Fe~0-PP-gAA),开展水中亚硝基二甲胺的去除研究.通过SEM、ICP-AES和XPS分析等对Pd/Fe~0/PP-g-AA进行表征.研究了不同制备条件和反应条件下,复合催化纤维对NDMA的降解性能.结果表明,丙烯酸单体质量分数为20%时,通过配位还原制备的复合催化纤维对NDMA的催化降解效果最佳,降解过程符合准一级反应动力学模型.在痕量浓度范围,NDMA初始浓度和溶液pH对复合纤维还原NDMA的性能影响不大.CO_3~(2-)和NO_3~-的存在显著抑制NDMA的降解,SO_4~(2-)、HCO_3~-和腐殖酸的存在对NDMA降解影响较小.     

Characterization of polycyclic aromatic hydrocarbon emissions from diesel engine retrofitted with selective catalytic reduction and continuously regenerating trap

Two after treatment units, selective catalytic reduction (SCR) and continuously regenerating trap (CRT), were independently retrofitted to a diesel engine, with the objective to investigate their impact on the conversion/reduction (CR) of polycyclic aromatic hydrocarbons (PAHs). The experiments were conducted under the European steady state cycle (ESC) first without any retrofits to get baseline emissions, and then with SCR and CRT respectively, on the same engine. The particulate matter (PM)-phase PAHs were trapped in fiberglass filters, whereas gas-phase PAHs were collected in cartridges, and then analyzed using a gas chromatograph-mass spectrometer (GC-MS). Both PM-phase and gas-phase PAHs were greatly reduced with CRT showing respective CR of 90.7% and above 80%, whereas only gas-phase PAHs were abated in the case of SCR, with CR of above 75%. Lower molecular weight (LMW) PAHs were in abundance, while naphthalene exhibited a maximum relative contribution (RC) to LMW-PAHs for all three cases. Further, the CR of naphthalene and anthracene were increased with increasing catalyst temperature of SCR, most likely due to their conversion to solid particles. Moreover, the Benzo[a]Pyrene equivalent (BaP_eq) of PAHs was greatly reduced with CRT, owing to substantial reduction of total PAHs.