团絮状双效催化聚苯硫醚滤料反应参数及机理

以N-油酰基多肽表面活化聚苯硫醚滤料,以酸性KMnO₄在60~80℃操作温度下正向滴定,在氧化作用下实现活性组分氧化.实验研究了催化滤料的低温NO还原和Hg⁰氧化性能,并通过SEM、EDX及TPD表征手段对催化滤料物化结构进行分析.分别考察了（0.9）Mn-Ce-Fe-Co-O_x/PPS反应体系温度、气相O₂浓度、初始NO浓度、氨氮比（NSR）、入口SO₂浓度的最佳反应参数.结果表明,有效组分MnO_x、CeO_x、CoO_x、Fe₂O₃以团絮状均匀分散在纤维表面;在反应温度170℃、O₂≥5%、NO≤500×10^-6、氨氮比1.0、SO₂≤100 500×10^-6条件下,催化滤料对NO还原及Hg⁰氧化效率基本达到80%左右;程序升温脱附实验Hg-TPD结果表明SO₂的Hg⁰氧化促进作用机理于SO₃与Hg⁰非均相反应优于SO₂硫酸化反应,而NO-TPD结果则表明NO与O₂在PPS表面相互作用类型以吸附态亚硝酸盐为主,吸附态NO₂次之.     

Catalytic activities of zeolite compounds for decomposing aqueous ozone

The advanced oxidation process (AOP), chemical oxidation using aqueous ozone in the presence of appropriate catalysts to generate highly reactive oxygen species, offers an attractive option for removing poorly biodegradable pollutants. Using the commercial zeolite powders with various Si/Al ratios and crystal structures, their catalytic activities for decomposing aqueous ozone were evaluated by continuously flowing ozone to water containing the zeolite powders. The hydrophilic zeolites (low Si/Al ratio) with alkali cations in the crystal structures were found to possess high catalytic activity for decomposing aqueous ozone. The hydrophobic zeolite compounds (high Si/Al ratio) were found to absorb ozone very well, but to have no catalytic activity for decomposing aqueous ozone. Their catalytic activities were also evaluated by using the fixed bed column method. When alkali cations were removed by acid rinsing or substituted by alkali-earth cations, the catalytic activities was significantly deteriorated. These results suggest that the metal cations on the crystal surface of the hydrophilic zeolite would play a key role for catalytic activity for decomposing aqueous ozone.     

铁铜催化剂非均相Fenton降解苯酚及机制研究

通过浸渍法制备了负载于活性炭(AC)上的金属催化剂Fe/AC、Cu/AC和Fe-Cu/AC,并通过X射线衍射(XRD)、物理吸附仪及X射线光电子能谱(XPS)对其进行了表征.研究了非均相Fenton反应催化H2O2降解苯酚废水的工艺参数,并通过中间产物分析和电子自旋共振谱(ESR)探讨了过程反应机制.实验表明,Cu/AC催化剂中铜主要以CuO形式存在,Fe/AC中铁以多价态形式存在,以无定形形态分散于活性炭中.Fe/AC、Cu/AC和Fe-Cu/AC催化过氧化氢降解苯酚60 min内降解率分别达到96.7%、77.5%和99%;Cu/AC和Fe-Cu/AC催化剂中活性组分铜和铁有一定溶出,而Fe/AC中活性组分铁溶出很少,苯酚降解主要是以非均相催化为主,同时在三轮循环实验后的苯酚降解率仍然高达93%以上,显示了良好的催化稳定性.在优化条件pH=3、T=303 K及初始H2O2为4.38 mmol.L-1下,Fe/AC催化过氧化氢对苯酚和TOC去除率分别达到97%和53%,没有催化剂时苯酚几乎不降解.ESR结果表明Fe/AC催化过氧化氢产生了羟基自由基,证明苯酚降解是以羟基自由基氧化为主;通过高效液相色谱(HPLC)检测苯酚降解中间产物主要有邻苯二酚、对苯二酚和对苯醌,推测苯酚降解途径主要为邻位和对位的羟基取代反应.     

硫毒化NH3-SCR脱硝催化剂再生方式的构建及机制研究

以CeTi复合氧化物负载NH₄HSO₄(模拟SO₂毒化催化剂)为研究对象,并向其中掺杂Mo作为改性组分,研究了硫毒化催化剂的再生过程与机制.与热再生相比,冷等离子体在再生毒化后催化剂的过程中显现出独特的优势.通过对再生后催化剂的物理化学性质表征及优化再生气氛,确认了冷等离子再生催化剂的优点：不仅能够保持催化剂物相结构的稳定,还可促进催化剂表面NH₄HSO₄的低温分解和硫物种的脱附.虽然冷等离子体再生后的催化剂NH₃-SCR反应活性下降,但可通过纯O₂气氛中焙烧的方式,实现对催化剂物理化学性质的重构和催化活性的再生.通过此研究,初步建立了催化剂“毒化-再生-重构”的基本构效关系,为硫中毒NH₃-SCR脱硝催化剂的再生提供了可行性方案.     

Recent progress on synthesis of ZIF-67-based materials and their application to heterogeneous catalysis

In recent years, an increasing amount of interest has been dedicated to the synthesis and application of ZIF-67-based materials due to their exceptionally high surface area, tunable porosity, and excellent thermal and chemical stabilities. This review summarizes the latest strategies of synthesizing ZIF-67-based materials by exploring the prominent examples. Then, the recent progress in the applications of ZIF-67-based materials in heterogeneous catalysis, including catalysis of the redox reactions, addition reactions, esterification reactions, Knoevenagel con-densations, and hydrogenation–dehydrogenation reactions, has been elaborately discussed. Finally, we end this work by shedding some light on the large-scale industrial production of ZIF-67-based materials and their applications in the future.     

压裂返排液的处理及回用

制备了沸石负载纳米TiO_2催化剂和蒙脱土负载纳米零价铁吸附剂,结合传统处理技术,构建了"絮凝—预氧化(Fenton氧化)—沸石负载纳米TiO_2催化臭氧氧化—蒙脱土载负纳米零价铁吸附"组合工艺,处理压裂返排液,考察了影响COD去除效果的因素。实验结果表明:在催化剂投加量1.0 g/L、臭氧通入时间5 min、吸附剂投加量5.0 g/L、吸附时间4 h的最佳条件下,COD从原水的4 032.60 mg/L降至37.03 mg/L,处理后出水各项指标均达到GB 8978—1996《污水综合排放标准》中的一级标准;80℃下,出水回用配制的压裂液黏度为4.4 mPa·s,高于自来水配制和压裂返排液配制的压裂液,耐温性有一定提升。     

芳烃石油树脂生产的环境保护

乙烯装置的副产品在综合利用中存在着严重的环境污染问题。中原油田采取了一些措施。用催化剂对生产尾气进行吸收,将有毒的氟化物转化为钙盐用于磷肥生产;将石油树脂聚合液中BF3脱除,防止对大气、水进行污染;用冷却回收工艺对减压蒸馏放空的芳烃气体进行处理。通过上述治理大大改善了企业的环境,有效地防止了环境污染。     

分子筛裂化催化剂的清洁生产工艺设计

系统地总结了分子筛裂化催化剂清洁工艺生产中已取得的主要进展。通过合理的工艺和工程设计，将生产中排放的大量污染物转化为可循环利用的资源，取得了环境效益和经济效益的双重回报。     

Directing technical change from fossil-fuel to renewable energy innovation: An application using firm-level patent data

In this paper we provide an analysis of directed technical change in the sector of electricity generation. We rely on patent data in fossil-fuel (FF) and renewable energy (REN) technologies for 5471 European firms over the 1978–2006 period. The novelty of our approach is in the focus on firm׳s heterogeneity in driving technological change. We make a distinction between small specialized firms, which innovate in only one type of technology, and large mixed firms, which innovate in both technologies, to analyse how REN patents can replace FF ones at the sector level both through a shift in innovation activities within existing firms and through firms׳ entry and exit. We use zero-inflated count data estimation techniques to identify the factors that affect specialized versus mixed firms׳ patenting behaviour both at the intensive (i.e., levels of innovation) and extensive (i.e., technological entry) margins. We further investigate the implications of our firm-level estimations for reducing the gap between REN and FF innovation at the aggregate level. We establish two key findings: (1) a decrease in the FF-REN technology gap mainly comes about through technological entry of specialized REN firms following an increase in REN market size; (2) increases in FF prices, FF market size, and FF knowledge stocks all increase the technology gap by increasing mixed firms FF innovation rates. An important implication of our results is that policies aimed at increasing REN innovation should focus on helping small firms to start and sustain innovation in the long-run.     

含镍废催化剂及其稳定化产物特性分析研究

该废催化剂呈不规则凝聚体,比表面积大,重金属Ni占比0.49％,几乎可以全部消解溶出.国标法下Ni浸出浓度为19.862 mg/L,随着浸出液pH值的降低而迅速增加;Ni浸出量随浸出时间的增加而增大,在10 h后逐渐趋于平稳.NaH2PO4、人造沸石、NTA、乙基黄原酸钾四种稳定化药剂对重金属Ni均有较好的稳定化效果,废催化剂表面形貌特征有显著变化,乙基黄原酸钾因螯合作用而稳定化效果最佳.水泥稳定化产物中重金属Ni在酸性下容易浸出,增容比为1.18,高于药剂稳定化.