Cu-Mn-Ce/分子筛催化剂吸附甲苯后的微波原位再生及床层温度分布探究

实验考察了Cu-Mn-Ce/分子筛催化剂吸附甲苯后的微波原位再生效果,分析了固定床温度场分布及催化剂多次再生后的吸附穿透曲线,并对Cu-Mn-Ce/分子筛催化剂进行了比表面积和表面形貌的表征测试.研究表明,微波功率117 W、空气流速0.5 m3·h-1和催化剂用量800 g下,吸附催化剂的微波再生效果良好,脱附甲苯在催化剂表面被氧化降解并使催化剂恢复吸附能力.再生时床层温度水平截面上由内向外缓慢降低,垂直方向从下而上逐渐升高,并在床层中上部达到最高的250~350℃.6次吸附穿透曲线和催化剂表征证实,微波原位再生时催化剂表面存在烧结与团聚现象,催化剂的比表面积和微孔体积有所减少,从而缩短了催化剂的穿透时间;微波再生2次后,催化剂结构趋于稳定,吸附穿透时间维持在70 min左右.研究发现,催化剂表面形貌和孔径的变化与床层温度场的分布呈正相关关系.     

1000MW燃煤电厂商业SCR脱硝催化剂的失活

以浙江某燃煤电厂1000MW商业SCR脱硝催化剂为研究对象,通过催化表征和活性评价综合分析该电厂1000MW商业SCR脱硝催化剂的失活原因.研究表明,催化剂的失活是多种因素共同作用的结果,（1） Fe,S,K和As元素中毒,其元素含量较新鲜催化剂分别增加了318.0%,233.3%,199.3%和99.8%;（2）催化剂表面孔道的飞灰堵塞,硫酸盐类沉积以及长时间高温反应造成催化剂的烧结和颗粒物的团聚,导致失活SCR脱硝催化剂比表面积较新鲜催化剂下降了20.3%;（3）活性组分V的价态变化造成V⁴⁺/V⁵⁺的比值由6.46下降至1.35,以及Lewis酸位点减少了34.2%,从而导致催化剂的失活.     

氢氧直接合成过氧化氢反应研究进展

重要化工原料过氧化氢的绿色、高效、安全制备工艺一直是研究热点之一。由氢气和氧气直接化合制备过氧化氢法(DSHP)具有过程简单、成本低等优点,受到了广泛关注。本文从原子层面反应机理、催化剂中贵金属的选取和复配效应、载体的组成和空间构型、反应介质的组成以及反应器中的流动控制等5个方面,总结近十年在利用微反应器实现DSHP反应方面的进展,并对该工艺的发展方向做出展望。     

Co、Ni掺入对Pd-Rh型催化剂三效净化C_3H_8、CO、NO的影响

以堇青石质陶瓷蜂窝为第一载体,活性氧化铝和铈锆复合氧化物固溶体涂层为第二载体,采用等体积浸渍法制备系列低Pd-Rh含量的三效催化剂及Co、Ni单或双掺入样品。主要研究了Co、Ni掺入对Pd-Rh型催化剂三效净化C3H8、CO、NO活性的影响,结果表明:同时掺入Co、Ni催化剂的三效净化效果优于单独掺入Co或Ni的三效净化效果,同时掺入Co、Ni时,掺入1%Co3O4和2%Ni O的催化剂净化效果最佳;350℃时,催化脱除C3H8、CO的效率分别为100%、97%,400℃时,催化脱除NO的效率为99%。     

Role of NO in Hg oxidation over a commercial selective catalytic reduction catalyst V2O5–WO3/TiO2

Experiments were conducted in a fixed-bed reactor that contained a commercial catalyst, V₂O₅–WO₃/TiO₂, to investigate mercury oxidation in the presence of NO and O₂. Mercury oxidation was improved by NO, and the efficiency was increased by simultaneously adding NO and O₂. With NO and O₂ pretreatment at 350°C, the catalyst exhibited higher catalytic activity for Hg⁰ oxidation, whereas NO pretreatment did not exert a noticeable effect. Decreasing the reaction temperature boosted the performance of the catalyst treated with NO and O₂. Although NO promoted Hg⁰ oxidation at the very beginning, excessive NO counteracted this effect. The results show that NO plays different roles in Hg⁰ oxidation; NO in the gaseous phase may directly react with the adsorbed Hg⁰, but excessive NO hinders Hg⁰ adsorption. The adsorbed NO was converted into active nitrogen species (e.g., NO₂) with oxygen, which facilitated the adsorption and oxidation of Hg⁰. Hg⁰ was oxidized by NO mainly by the Eley–Rideal mechanism. The Hg⁰ temperature-programmed desorption experiment showed that weakly adsorbed mercury species were converted to strongly bound ones in the presence of NO and O₂.     

以TiO2为载体的锰铈系低温SCR脱硝催化剂抗硫抗水性能研究进展

开发具有低温、高活性、高抗硫抗水性的NH₃-SCR脱硝催化剂成为目前广大学者的主要研究方向。锰铈催化剂因为其优异的低温活性而具有广阔的应用前景,但反应气氛中的SO₂和H₂O会使催化剂中毒。本文分析了以TiO₂为载体的锰铈基催化剂在低温氨选择性催化还原过程中SO₂和H₂O的中毒机理,重点从添加助剂和改变催化剂形貌两方面介绍了提高锰铈催化剂抗硫抗水性的研究进展。最后针对目前锰铈催化剂存在的问题对其研究方向进行了展望。     

Fe2O3-CeO2-Bi2O3/γ-Al2O3 catalyst in the catalytic wet air oxidation (CWAO) of cationic red GTL under mild reaction conditions

Fe₂O₃-CeO₂-Bi₂O₃/γ-Al₂O₃, an environmental friendly material, was investigated. The catalyst exhibited good catalytic performance in the CWAO of cationic red GTL. The apparent activation energy for the reaction was 79 kJ·mol⁻¹. HO₂· and O₂·⁻ appeared as the main reactive species in the reaction. The Fe₂O₃-CeO₂-Bi₂O₃/γ-Al₂O₃ catalyst, a novel environmental-friendly material, was used to investigate the catalytic wet air oxidation (CWAO) of cationic red GTL under mild operating conditions in a batch reactor. The catalyst was prepared by wet impregnation, and characterized by special surface area (BET measurement), X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS). The Fe₂O₃-CeO₂-Bi₂O₃/γ-Al₂O₃ catalyst exhibited good catalytic activity and stability in the CWAO under atmosphere pressure. The effect of the reaction conditions (catalyst loading, degradation temperature, solution concentration and initial solution pH value) was studied. The result showed that the decolorization efficiency of cationic red GTL was improved with increasing the initial solution pH value and the degradation temperature. The apparent activation energy for the reaction was 79 kJ·mol⁻¹. Hydroperoxy radicals (HO₂·) and superoxide radicals (O₂⁻·) appeared as the main reactive species upon the CWAO of cationic red GTL.     

Ce(x)Mn/TiO2-y催化剂低温NH3-SCR脱硝性能

以锐钛矿TiO₂(P25)为载体采用原位生长法负载锰氧化物制备了Mn/TiO₂催化剂,再以等体积浸渍-煅烧法对该催化剂掺杂氧化铈制备Ce(x)Mn/TiO₂-y催化剂用以烟气低温SCR脱硝.在固定锰负载量(质量分数为8%)的基础上,考察了铈掺杂量(铈锰摩尔比)、煅烧温度对催化剂SCR脱硝性能的影响.采用TEM、BET、XRD和XPS等手段表征了催化剂的理化结构特性.结果发现,当Ce/Mn的摩尔比例为1.0,煅烧温度为300℃时,Ce(1.0)Mn/TiO₂-300催化剂在150—300℃温度范围内、10500—27000 h^-1的空速范围内,能够保持90%以上的NO转化率.理化性能分析结果表明,煅烧温度对催化剂的微观形貌影响显著,随着煅烧温度的升高,Ce(1.0)Mn/TiO₂-500催化剂活性物种颗粒集聚明显、比表面积降低,且锰氧化物价态分布偏向于低价态;铈的掺杂有助于Ce(1.0)Mn/TiO₂-300催化剂活性物种在载体表面的均匀分散,可以促进产生更多的Mn4+物种和更多的吸附氧,有利于催化剂低温SCR脱硝性能的提升.     

介孔ZnO负载Fe-Cu-Zr复合催化剂用于催化燃烧降解乙酸丁酯

采用醇热法制备了有序球状介孔ZnO负载Fe-Cu-Zr复合催化剂,应用BET、SEM、XRD、XPS等对不同物质的量比催化剂进行了表征,研究了催化降解乙酸丁酯的活性及其影响因素,并推测了降解机理.结果表明,铁铜锆复合催化剂颗粒均匀,分散性较好,孔径大部分小于50 nm,比表面积为46~68 m²·g^-1.各活性成分能够共存和协同发挥作用,铁、铜、锆离子吸附在氧化锌晶胞内,粒子间量子作用力促使晶胞表面积略有变大.锆能够提高3种活性成分间的作用力,可以调节表面电子密度,促使结合能向低的方向偏移,增强催化剂的氧化还原能力.随着锆比例的增大,催化剂的活性也随之增强;随着初始浓度、空速、相对湿度的增加,乙酸丁酯降解效率均有所下降.在乙酸丁酯初始浓度为2590 mg·m^-3、空速为9000 h^-1的工况下,ZnO-3M催化剂降解乙酸丁酯的T₅₀为116 ℃,T₉₀为200 ℃,270 ℃时CO₂转化率达96%,具有良好的低温催化活性和稳定性.乙酸丁酯催化氧化主要中间产物为少量的低级酸和低碳醇,最后被彻底氧化成CO₂和H₂O.     

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.