MTO废催化剂SAPO-34的再生

采用干凝胶转化法对甲醇制烯烃(MTO)废催化剂SAPO-34进行再生,将SAPO-34分子筛晶化所需的硅、铝、磷原料同时作为黏结剂使用,经干凝胶转化制备出再生催化剂,并对催化剂进行了表征及MTO反应活性评价。表征结果显示,再生催化剂的晶体结构、微观形貌、粒径分布、孔结构、耐磨性及酸中心均得到了恢复与改善,磨损指数可达0.35%/h。实验结果表明:在催化剂加入量为1.0 g、进气中甲醇质量分数为95%、甲醇质量空速为3 h-1、反应温度为450℃、反应压力为常压的条件下,再生催化剂的甲醇转化率接近100%,双烯(乙烯和丙烯)选择性较废催化剂提高了约3百分点,可达87%以上;同时,再生催化剂的寿命也较废催化剂有了明显改善。     

Ni,Co掺杂对Mn-Ce/TiO_2催化剂脱硝活性的影响

以Ti O_2为载体,采用浸渍法制备Ni或Co掺杂的Mn-Ce/Ti O_2催化剂,用于烟气的选择性催化还原法低温脱硝。考察Ni或Co的掺加对Mn-Ce/Ti O_2催化剂活性的影响,并对各催化剂进行了BET,XRD,H_2-TPR,XPS表征。实验结果表明:在NO,NH_3,O_2的体积分数分别为6×10~(-4),6×10~(-4),6×10~(-2),空速为16 000 h~(-1)的条件下,Mn-Ce/Ti O_2、Mn-Ce-Ni_(0.4)/Ti O_2和Mn-Ce-Co_(0.2)/Ti O_2催化剂的NO去除率在120℃时分别为38%,68%,74%,在150℃时分别为64%,92%,近100%,这表明掺加Ni或Co后Mn-Ce/Ti O_2催化剂的脱硝活性明显提高;在进气中加入体积分数为1×10~(-4)的SO_2后,Mn-Ce/Ti O_2催化剂的NO去除率在300 min内从98.2%下降至57.2%,而Mn-CeCo_(0.2)/Ti O_2和Mn-Ce-Ni_(0.4)/Ti O_2催化剂的NO去除率分别为73.9%和69.8%,这表明Ni或Co的掺加有助于提高催化剂的抗硫性能。表征结果表明:Ni或Co的掺加基本不影响Mn和Ce在载体Ti O_2上的分散;Ce元素以Ce~(3+)和Ce~(4+)价态存在,且主要为Ce~(4+);催化剂的比表面积变化不大;Mn O_x与Ce O_x的结晶度降低,催化剂的氧化还原能力增强。     

Interfacial mechanisms of heterogeneous Fenton reactions catalyzed by iron-based materials: A review

The heterogeneous Fenton reaction can generate highly reactive hydroxyl radicals(·OH)from reactions between recyclable solid catalysts and H_2O_2 at acidic or even circumneutral pH.Hence,it can effectively oxidize refractory organics in water or soils and has become a promising environmentally friendly treatment technology.Due to the complex reaction system,the mechanism behind heterogeneous Fenton reactions remains unresolved but fascinating,and is crucial for understanding Fenton chemistry and the development and application of efficient heterogeneous Fenton technologies.Iron-based materials usually possess high catalytic activity,low cost,negligible toxicity and easy recovery,and are a superior type of heterogeneous Fenton catalysts.Therefore,this article reviews the fundamental but important interfacial mechanisms of heterogeneous Fenton reactions catalyzed by iron-based materials..OH,hydroperoxyl radicals/superoxide anions(HO_2./O_2~-.)and high-valent iron are the three main types of reactive oxygen species(ROS),with different oxidation reactivity and selectivity.Based on the mechanisms of ROS generation,the interfacial mechanisms of heterogeneous Fenton systems can be classified as the homogeneous Fenton mechanism induced by surface-leached iron,the heterogeneous catalysis mechanism,and the heterogeneous reaction-induced homogeneous mechanism.Different heterogeneous Fenton systems catalyzed by characteristic iron-based materials are comprehensively reviewed.Finally,related future research directions are also suggested.     

Removing lignin model pollutants with BiFeO3–g-C3N4 compound as an efficient visible-light-heterogeneous Fenton-like catalyst

BiFeO_3–g-C_3N_4 nanoscaled composite was prepared with a hydrothermal method and evaluated as a highly efficient photo-Fenton like catalyst under visible light irradiation. The BiFeO_3–g-C_3N_4 composite exhibited much stronger adsorption ability to lignin model pollutant(guaiacol) than that of BiFeO_3, which may be due to the higher specific surface area(BiFeO_3–g-C_3N_4: 35.59 m~2/g BiFeO_3: 7.42 m~2/g) and the adsorption form of π–π stack between g-C_3N_4 and guaiacol. The composite exhibited excellent visible light-Fenton like catalysis activity, being influenced by the solution pH value and the proportions of BiFeO_3 and g-C_3N_4 nanosheets. Under optimal conditions with visible light irradiation, the BiFeO_3–g-C_3N_4 composite yielded fast degradation of guaiacol with an apparent rate constant of 0.0452 min~(-1), which were 5.21 and 6.80 folds of that achieved by using BiFeO_3 and the mixture of BiFeO_3 and g-C_3N_4 nanosheets, respectively. The significantly enhanced visible light-Fenton like catalytic properties of the BiFeO_3–g-C_3N_4 composite in comparison with that of BiFeO_3 was attributed to a large surface area, much increased adsorption capacity and the semiconductor coupling effect between BiFeO_3 and g-C_3N_4 in the composite.     

氧化催化转化器对甲醇压燃尾气中甲醛排放的影响

在一台经过改装的压燃式发动机上,采用柴油/甲醇组合燃烧(DMCC)模式进行了台架实验,利用气相色谱分析技术检测了1800r·min<'-1时发动机尾气中甲醛的排放特性,对比研究了负荷、甲醇掺烧比、排气温度.催化转化器对甲醛排放的影响.研究结果表明,在压燃式发动机上采用DMCC模式,低负荷运行时,尾气中甲醛含量随甲醇掺烧比的增加而增多,在甲醇掺烧比为46%时.甲醛排放量达到180 x 10<'-6(体积分数),催化后可以减少25%～45%;在中,高负荷运行时.甲醛排放量随甲醇掺烧比的变化基本不变,高负荷比中负荷运行时甲醛排放稍高.但尾气经催化处理后,甲醛排放反而增加,最高增加1倍.催化转化器的转化效果与排气温度密切相关,当排气温度在大约300°C以下时,催化转化器可以降低甲醛排放量;当温度为300°C～410°C时,催化后尾气中的甲醛排放较催化前有所增加;当排气温度高于425°C时.催化后尾气中甲醛排放显著减少.     

焙烧温度对催化剂Cu-Ni-Ce/SiO2性能的影响

采用浸渍法在不同焙烧温度下制备了用于湿式H202降解吡虫啉农药废水的Cu-Ni-Ce/SiO2催化剂,利用TG、BET、XRD和XPS等对其进行了表征,研究了焙烧温度对催化剂表面结构的影响以及催化剂表面结构与活性及稳定性之间的关系.结果表明:降低焙烧温度,cu、Ni、ce之间的相互作用使得催化剂晶粒尺寸减小,比表面积增加,Cu、Ni固溶体量和催化剂表面化学吸附氧量增加.湿式H,O,降解吡虫啉农药废水时,600℃下焙烧获得的Cu-Ni-Ce/Si02催化剂活性最高;在催化剂用量10 g·L-1、反应温度为110℃、双氧水用量为理论需用量、进水pH为9.0、反应时间为60 min的条件下,COD去除率为91.5%,活性组分溶出量较小.研究结果表明,焙烧温度对CuO、NiO、CeO,及Cu、Ni固溶体之间的相瓦作用有较大影响,从而影响了催化剂湿式降解吡虫啉农药废水的活性和稳定性.     

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。     

重铬酸钾法测定化学需氧量的实验条件优化

以降低成本、减少二次污染、提供多元化实验条件为主要出发点,开展GB 11914-89中氯离子掩蔽剂加入量和催化剂种类等优化实验研究。结果表明:采用按比例加入的方式可以降低硫酸汞使用量,m[HgSO4]:m[Cl-]=10∶1即可达到有效掩蔽效果;在标准样品、地表水和一般废水的COD测定中,硫酸镍、硫酸铝钾和磷酸二氢锰作为硫酸银的替代物具有一定的可行性,建议最低加入量为4g/L。     

燃煤机组SCR脱硝催化剂的研究进展

选择性催化还原(SCR)是目前控制氮氧化物排放的主要技术。本文介绍了锅炉炉后脱硝系统的布置位置及工艺条件、已经工业化的氨选择性高温还原钒催化剂的特点,以及近年来低温脱硝催化剂的研究现状。指出我国脱硝催化剂应提高还原剂的选择性,开发新型低温催化剂应重点考察烟气中的水、二氧化硫及硫酸氢铵等对催化剂的影响。     

商用V/W/Ti系脱硝催化剂表面SO3生成的反应机理

基于燃煤烟气SO₃生成与排放给电厂运行及大气环境带来的严重影响,研究了一种在役典型商用蜂窝型V/W/Ti系脱硝催化剂表面的SO₃生成反应动力学及反应机理.结果表明,反应温度与SO₂浓度是影响催化剂表面SO₃生成的关键因素.在SO₂浓度为400×10^-6时,当反应温度从300℃升至360℃,SO₂-SO₃转化率从0.2%提高至0.65%,温度达到400℃后,催化剂表面V₂O₅活性增加更为显著,SO₂-SO₃转化率从0.65%增2.3%,SO₃生成反应的表观速率常数增加近3倍.SO₃在催化剂表面的生成路径为：SO₂与V⁵⁺-OH反应生成中间产物VOSO₄与HSO₄^-,随后进一步反应生成SO₃.SO₂主要通过其在催化剂表面的吸附、转化过程影响SO₃的生成,其本征动力学反应级数为0.52.O₂的本征动力学反应级数为0,SO₃生成反应可以在无O₂条件下进行,O₂存在会促进反应进行,但不会改变反应路径.