NO在分子筛ZSM-5催化剂上催化氧化动力学研究

研究了常温下NO在疏水型高硅分子筛ZSM-5上的氧化反应. 结果发现,NO在分子筛ZSM-5表面氧化的同时,伴随着明显的吸附过程,待吸附饱和后释放出NO2.相比于活性炭,高硅分子筛ZSM-5上NO氧化受水汽影响较小,303K饱和湿气下,NO稳态转化率只比干气下降低6%.在排除内、外扩散影响的条件下,于等温积分反应器中研究了稳定阶段NO氧化的本征动力学,根据不同温度下X~W/FA0及NO分压数据,计算了反应速率,建立简化的动力学模型并获得了反应速率方程,结果表明其拟合复相关系数较高.     

疏水型H-ZSM-5分子筛上NO氧化反应的研究

针对NO低温氧化催化剂的抗水汽性差的问题,以疏水型高硅H-ZSM-5分子筛为NO氧化催化剂,在温度为10~90℃、NO进口浓度为0.05%~0.08%,及相对湿度为0~100%条件下,考察了NO的氧化反应.结果表明,H-ZSM-5分子筛的硅铝比由50提高至300时,湿气条件(水汽含量1.18%)下,NO氧化率由20%升高至56%;干气下,低温有利于NO氧化;湿气下(水汽含量1.18%),NO氧化率随着温度的升高先增加后减少,最佳反应温度为20℃,与NOx工业废气的排放温度相近.200h的稳定性试验结果显示,在30℃、NO进口浓度0.08%、空时0.5s、保持相对湿度为50%或100%时,NO氧化率可维持在60%和50%,催化剂具有良好的稳定性.     

选择性催化氧化NO的催化剂研究进展

工业生产过程产生的NO对大气环境造成严重污染.选择性催化氧化吸收法(SCO)脱硝是目前较有价值的脱硝技术.选择性催化氧化的关键在于催化剂的选择.目前,用于NO催化氧化的催化剂主要有活性炭类、分子筛类、贵金属类、过渡金属氧化物类催化剂.其中,过渡金属氧化物类催化剂具有良好的催化活性,价格低廉,制作简单等,是目前较有研究前...     

CuAPO-5分子筛催化氧化水溶液中苯酚的性能

以水热晶化法合成了铜磷铝分子筛CuAPO-5，并用XRD、SEM，FT—IR，UV—Vis等对样品进行了表征，结果表明Cu^2＋进入到了AlPO4-5分子筛骨架中。研究了以CuAPO-5为催化剂，H2O2为氧化剂对水溶液中苯酚的催化氧化性能。在苯酚初始浓度200mg／L、H2O2添加量1200mg／L、pH值5．0、处理温度80℃时，处理240min时苯酚去除率达到100％，TOC去除率达81．76％，析出到溶液中Cu^2＋浓度仅为0．527mg／L。温度从40℃上升到80℃时，苯酚的去除率及TOC去除率明显增大，表明温度对催化剂的活性影响显著，相比于均相催化剂骨架Cu催化过氧化氢分解需要更多的能量。重复性实验表明，催化剂性能稳定。     

NO催化氧化的初步研究

利用一套小型动态试验装置进行配气实验，分析了一系列金属氧化物对气体中低浓度ＮＯ转化率的催化活性顺序为Ｃｒ＞Ｆｅ＞Ｃｏ＞Ｍｎ＞Ｃｕ，并对其综合影响进行了分析。通过实验总结出适宜的反应条件及催化剂配方，为以后研究提供了重要的数据资料。     

氧化锰八面体分子筛的合成及其对苯催化氧化性能

采用回流的方法,制备了氧化锰八面体分子筛（OMS-2）纳米棒.利用X射线衍射（XRD）、扫描电子显微镜（SEM）、氮气吸附-脱附、程序升温还原（H2-TPR）分别对产物进行晶型、形貌、孔径和H2还原性能进行分析,并考察不同煅烧温度下的催化剂对苯的催化氧化性能及300℃煅烧催化剂的稳定性.结果表明,煅烧温度对氧化锰八面体分子筛（OMS-2）的表面特征有显著的影响,煅烧温度越高,比表面积和孔容越小,平均孔径越大.同时随着煅烧温度的增加,催化剂对苯的催化氧化性能降低.经300℃煅烧的催化剂对苯的催化活性最佳,反应温度为200℃时,苯的转化率达到了50%;当反应温度为250℃时,苯的转化率达到90%.经300℃煅烧的催化剂在260℃下70 h内,对苯的催化氧化性能降低了5%,具有良好的稳定性.     

ZSM-5分子筛疏水改性及催化H_2O_2氧化苯酚的性能研究

以甲苯为溶剂、三甲基氯硅烷(TMCS)为表面改性剂,采用液相接枝的方法对ZSM-5分子筛进行疏水化改性,通过XRD、FTIR、N2吸附-脱附、TG、水静态吸附试验等手段对改性前后的ZSM-5分子筛进行了表征,并将其应用于苯酚的吸附及催化氧化研究。结果表明:改性后ZSM-5分子筛仍保持原有的孔道结构,-Si(CH3)3基团接枝到孔道表面,使比表面积和孔容、孔径均有下降;改性后ZSM-5分子筛水静态吸附率由3.82%降至1.12%,疏水性得到明显提高;改性后ZSM-5分子筛对苯酚的吸附机理符合Langmuir模型,吸附动力学符合准二级动力学模型,且对水中苯酚的饱和吸附量由30.7mg/g增加到36.9mg/g;疏水改性后的分子筛负载MnO2催化H2O2氧化降解苯酚的效率可达86.2%,且其吸附过程与催化氧化过程具有协同效应。     

SBA-15介孔分子筛负载金属酞菁催化氧化甲醛

采用浸渍法将钴或铁酞菁组装进有序介孔材料SBA-15中,通过XRD和N₂吸附方法对组装体进行了表征,研究了常温常压下,该组装体催化氧化甲醛的活性.结果表明,组装体具有优良的处理甲醛性能.钴酞菁比铁酞菁组装体的催化氧化活性高;钴和铁酞菁的协同作用使组装体具有更强的催化氧化活性,当二者摩尔比为1:1时,催化氧化活性最高;并借鉴金属酞菁处理有机巯醇的原理探讨了金属酞菁催化氧化甲醛的原理.     

烟气条件对直流电晕自由基簇射NO氧化过程的影响

运用以湿空气为自由基源物质的直流电晕自由基簇射系统,研究了烟气在反应器内的滞留时间、烟气流速和NO浓度对NO氧化过程的影响.结果表明:烟气流速的增加会抑制电晕放电的发展,而烟气中NO浓度的增加则使放电变得更加容易.NO的氧化受烟气在反应器内滞留时间的影响较小,而它受烟气流速的影响较大.在2W的输入功率下,当烟气在反应器内的滞留时间从8.5s增加到34.2s时,NO的氧化率只从54.5 %提高到57.6 %.而在1.7W·h/m³的能量密度下,当烟气流速从1.4cm/s增加到6.3cm/s时,NO的氧化率从60.0%减少到38.6%,能量利用率也从20.8g/(kW·h)下降到了13.3g/(kW·h).在湿空气流量一定的情况下,NO初始浓度存在一个最佳值,本实验中最佳的NO浓度为100×10^-6左右.     

H_2O和SO_2对Cr-Ce/TiO_2催化氧化NO性能的影响

采用浸渍法在最佳制备条件下制备了新型Cr-Ce/TiO2催化剂,并对催化剂进行了BET和XRD表征.同时,考察了反应温度、H2O和SO2对该催化剂催化氧化NO性能的影响,并对中毒催化剂进行了FT-IR分析,讨论了中毒机理.结果表明,Cr-Ce/TiO2催化剂具有良好的NO氧化活性,在空速为10000h-1、O2体积分数8%(φ)、NO进口体积分数700×10-6条件下,反应温度250℃时NO转化率可达到59.7%,330℃时NO转化率可达到最大值80.7%.单独加入10%(φ)H2O或300×10-6(φ)SO2都可使催化剂活性降低,但在较高温度时影响较小.330℃下单独通入SO2和同时通入H2O与SO210h后,由于催化剂表面生成了少量硫酸盐和亚硫酸盐,活性下降并维持在62.4%左右,能够满足对NOx进行高效吸收的要求;停止通入H2O和SO2后,催化剂活性恢复到71.6%,加热处理后活性能进一步恢复到78.5%.该催化剂具有比文献中报道的其它NO氧化催化剂更强的抗H2O和SO2毒化能力.     

汽车尾气净化催化剂Ag-ZSM-5选择性催化还原NO

评价了Ag-ZSM-5分子筛催化剂选择性还原NO的活性,并运用原位漫反射红外光谱研究NO在该催化剂上的选择性还原机理.结果表明,以丙烯为还原剂,有O₂(3.6%)存在时,Ag-ZSM-5有良好活性,在773K时N₀还原成N2的转化率达68.8%.基于漫反射红外光谱,认为N₀还原为N2的过程中,NO以NO_x吸附态形式与丙烯的活化物种C_xH_y或C_xH_yO_z反应,生成有机-氮氧化物(R-NO₂或R-ONO)中间体,再进一步反应,最终生成N₂;催化剂表面形成有机-氮氧化物是关键步骤,Ag的作用是促进形成NO_x,O₂ 的作用是促进C₃H₆活化及NO转化成Nox,并且O₂是有效产生有机-氮氧化物不可缺少的条件.     

Review on the NO removal from flue gas by oxidation methods

Due to the increasingly strict emission standards of NOx on various industries, many traditional flue gas treatment methods have been gradually improved. Except for selective catalytic reduction (SCR) and selective non-catalytic reduction (SNCR) methods to remove NOx from flue gas, theoxidation method is paying more attention to NOx removal now because of the potential to simultaneously remove multiple pollutants from flue gas. This paper summarizes the efficiency, reaction conditions, effect factors, and reaction mechanism of NO oxidation from the aspects of liquid-phase oxidation, gas-phase oxidation, plasma technology, and catalytic oxidation. The effects of free radicals and active components of catalysts on NO oxidation and the combination of various oxidation methods are discussed in detail. The advantages and disadvantages of different oxidation methods are summarized, and the suggestions for future research on NO oxidation are put forward at the end. The review on the NO removal by oxidation methods can provide new ideas for future studies on the NO removal from flue gas.     

催化氧化NO催化剂Mn/ZrO2的制备与性能研究

以二氧化锆为载体负载锰氧化物,制备了MnO x/ZrO2催化剂用于催化氧化法(SCO)脱除烟气NO,考察了制备条件和反应条件对催化剂SCO活性的影响.同时,采用N2吸附、SEM、XRD及XPS等手段对催化剂理化性质进行了表征.结果表明,采用等体积浸渍法,以硝酸锰作为前驱体制备的Mn8/ZrO2/450催化剂在300℃、空速15000 h-1条件下,NO转化率可达84%,表现出较好的NO氧化活性.催化剂的主要活性组分为MnO2,在催化剂载体表面上呈现出较好的分散度.对催化剂进行了NO等温吸附与程序升温脱附,结合程序升温表面反应(TPSR)实验,探讨了催化剂表面NO催化氧化机理.研究发现,NO在该催化剂表面主要以吸附态反应,在含氧气氛中吸附态NO的氧化速率高于脱附速率,表面NO2的脱附峰温与最佳SCO活性温度相吻合.上述结果表明,NO转化过程速率受氧化产物NO2的脱附步骤控制,表面反应为快速步骤.     

老化对钴铈基催化剂催化氧化丙烷的影响

采用柠檬酸络合法合成Co-CeOx多活性中心催化剂,在不同温度进行加速老化处理,测试新鲜和老化后催化剂对丙烷的催化氧化性能,同时对其结构和性质进行表征.结果表明,当加速老化温度低于650℃时,丙烷转化率达50％的温度变化幅度小于10℃;加速老化温度高于750℃时,催化剂氧化丙烷的性能快速下降.表征结果显示,Co-CeO...     

不同母体制备的金属离子交换ZSM-5分子筛上C_3H_6选择催化还原NO反应的研究

 研究了由钠型及氢型ZSM-5母体制备的金属离子交换分子筛在过量氧存在下丙烯选择催化还原NO的反应。发现反应活性及活性温度范围取决于分子筛母体与金属离子的种类。在各种金属离子交换分子筛催化剂中，钴离子交换CoH－ZSM－5具有最高的活性，且随钴离子交换度的增加反应活性亦随之增加。     

Complete catalytic oxidation of o-xylene over CeO2 nanocubes

The activities of CeO2 nanocubes calcined at di erent temperatures were tested for catalytic oxidation of o-xylene. Using CeO2 nanocubes as catalysts, complete catalytic oxidation of o-xylene was achieved below 210°C. The CeO2 nanomaterials were characterized by means of BET, X-ray di raction (XRD), transmission electron microscopy (TEM), and high-resolution transmission electron microscopy (HRTEM). From the TEM images, all CeO2 nanocubes displayed cubic morphology irrespective of calcination temperature. The HRTEM images revealed that these nanocubes were enclosed by reactive f001g planes, which may contribute to the intrinsically catalytic property of o-xylene oxidation. The higher activity of CeO2 nanocubes calcined at 550°C than those calcined at above 550°C was attributed to their smaller crystallite size and larger surface area. The influences of reaction conditions were also studied, which found that a higher reaction temperature was necessary for complete catalytic oxidation of o-xylene at higher weight hourly space velocity (WHSV) and o-xylene concentration.     

Complete catalytic oxidation of o-xylene over Ce02 nanocubes

The activities of CeO2 nanocubes calcined at different temperatures were tested for catalytic oxidation of o-xylene. Using CeO2 nanocubes as catalysts, complete catalytic oxidation of o-xylene was achieved below 210℃. The CeO2 nanomaterials were characterized by means of BET, X-ray diffraction (XRD), transmission electron microscopy (TEM), and high-resolution transmission electron microscopy (HRTEM). From the TEM images, all Ce02 nanocubes displayed cubic morphology irrespective of calcination temperature. The HRTEM images revealed that these nanocubes were enclosed by reactive {001}planes, which may contribute to the intrinsically catalytic property of o-xylene oxidation. The higher activity of Ce02 nanocubes calcined at 550℃ than those calcined at above 550℃ was attributed to their smaller crystallite size and larger surface area. The influences of reaction conditions were also studied, which found that a higher reaction temperature was necessary for complete catalytic oxidation of o-xylene at higher weight hourly space velocity (WHSV) and o-xylene concentration.     

Effects of metal and acidic sites on the reaction by-products of butyl acetate oxidation over palladium-based catalysts

Catalytic oxidation is widely used in pollution control technology to remove volatile organic compounds. In this study, Pd/ZSM-5 catalysts with different Pd contents and acidic sites were prepared via the impregnation method. All the catalysts were characterized by means of N2 adsorption- desorption, X-ray fluorescence （XRF）, HE temperature programmed reduction （H2-TPR）, and NH3 temperature programmed desorption （NH3-TPD）. Their catalytic performance was investigated in the oxidation of butyl acetate experiments. The by-products of the reaction were collected in thermal desorption tubes and identified by gas chromatography/mass spectrometry. It was found that the increase of Pd content slightly changed the catalytic activity of butyl acetate oxidation according to the yield of CO2 achieved at 90%, but decreased the cracking by-products, whereas the enhancement of strong acidity over Pd-based catalysts enriched the by-product species. The butyl acetate oxidation process involves a series of reaction steps including protolysis, dehydrogenation, dehydration, cracking, and isomerization. Generally, butyl acetate was cracked to acetic acid and 2- methylpropene and the latter was an intermediate of the other by-products, and the oxidation routes of typical by-products were proposed. Trace amounts of 3-methylpentane, hexane, 2-methylpentane, pentane, and 2-methylbutane originated from iso4merization and protolysis reactions.