Activities of different metal oxide catalysts on NO reduction and CO oxidation

A series of transition metal oxide catalysts (Zn, Ti, Cu, Ni, Fe and V) supported on Al₂O₃ and SiO2 were prepared using the incipient wetness impregnation method. Their performances on NO reduction and CO oxidation followed the sequence of TiO₂ > CuO/ZnO > CuO > ZnO. TiO₂ supported on SiO₂ was more active than that on Al₂O₃, while ZnO had the opposite performances. The activities of CuO/Al₂O₃ and ZnO/SiO₂ were both decreased with the calcination temperature increasing because the sintering and agglomerations of catalysts were occurred at high temperature.     

CeO_x/AC催化剂NH_3选择性催化还原NO

以用不同浓度的HNO3预处理后的椰壳活性炭为载体,负载铈制备SCR催化剂。利用比表面积分析仪（BET）、X射线衍射（XRD）、扫描电镜（SEM）和催化剂活性实验,探讨了不同变量如金属离子的分布、焙烧温度和载体属性对催化活性的影响。结果表明,HNO3处理后,经500℃焙烧金属铈负载量为7%的催化剂表现出优良的催化性能。在90℃时,NO转化率在90%以上,随温度升高,达到接近100%的NO转化率。     

Cobalt-based alumina pillared zirconium phosphate catalysts for the selective catalytic reduction of NO by propane

A series of cobalt containing alumina pillared zirconium phosphate materials have been prepared by ion exchange or by impregnation, and fully characterised. The catalytic behaviour of these materials in the selective catalytic reduction of NO by propane, in excess of oxygen, at temperatures ranging between 350 and 550 degrees C, has been also evaluated. A maximum NO conversion close to 14% is obtained on Co-impregnated catalysts heated at 600 degrees C. The NO reduction seems to be related to the presence of Co3+, thus the calcination temperature of samples influences the resulting activity much more than the cobalt content.     

Cu/Al-PILC催化的C3H6选择还原NO反应的研究

采用聚合羟基铝交联剂对蒙脱土进行撑柱,合成铝交联黏土(Al-PILC),并以其为载体,制备了应用于C3H6选择还原NO的催化剂Cu/Al-PLIC.考察了制备工艺条件及La2O3助剂对催化剂性能的影响,并采用DTA、IR技术对Al-PILC进行表征.研究结果表明,Al-PILC热稳定性随Al/clay比增加逐步提高,SO2-4改性Al-PILC上SO2-4与铝氧化柱形成了具有超强酸性的结构,催化活性得到显著提高;当Al/clay比为10 mmol/g,浸渍SO2-4量为20%(wt),Cu担载量为3%(wt),空速20 000 h-1时,Cu/Al-PILC在350℃NO转化率达到最大值52.02%;浸渍0.5%La2O3提高了Cu/Al-PILC催化剂的活性和热稳定性.     

CeOx/AC催化剂NH3选择性催化还原NO

以用不同浓度的HNO3预处理后的椰壳活性炭为载体,负载铈制备SCR催化剂。利用比表面积分析仪(BET)、X射线衍射(XRD)、扫描电镜(SEM)和催化剂活性实验,探讨了不同变量如金属离子的分布、焙烧温度和载体属性对催化活性的影响。结果表明,HNO3处理后,经500℃焙烧金属铈负载量为7%的催化剂表现出优良的催化性能。在90℃时,NO转化率在90%以上,随温度升高,达到接近100%的NO转化率。     

A predictive mechanism for mercury oxidation on selective catalytic reduction catalysts under coal-derived flue gas

This paper introduces a predictive mechanism for elemental mercury (Hg(o)) oxidation on selective catalytic reduction (SCR) catalysts in coal-fired utility gas cleaning systems, given the ammonia (NH3)/nitric oxide (NO) ratio and concentrations of Hg(o) and HCl at the monolith inlet, the monolith pitch and channel shape, and the SCR temperature and space velocity. A simple premise connects the established mechanism for catalytic NO reduction to the Hg(o) oxidation behavior on SCRs: that hydrochloric acid (HCl) competes for surface sites with NH3 and that Hg(o) contacts these chlorinated sites either from the gas phase or as a weakly adsorbed species. This mechanism explicitly accounts for the inhibition of Hg(o) oxidation by NH3, so that the monolith sustains two chemically distinct regions. In the inlet region, strong NH3 adsorption minimizes the coverage of chlorinated surface sites, so NO reduction inhibits Hg(o) oxidation. But once NH3 has been consumed, the Hg(o) oxidation rate rapidly accelerates, even while the HCl concentration in the gas phase is uniform. Factors that shorten the length of the NO reduction region, such as smaller channel pitches and converting from square to circular channels, and factors that enhance surface chlorination, such as higher inlet HCl concentrations and lower NH3/NO ratios, promote Hg(o) oxidation. This mechanism accurately interprets the reported tendencies for greater extents of Hg(o) oxidation on honeycomb monoliths with smaller channel pitches and hotter temperatures and the tendency for lower extents of Hg(o) oxidation for hotter temperatures on plate monoliths. The mechanism also depicts the inhibition of Hg(o) oxidation by NH3 for NH3/NO ratios from zero to 0.9. Perhaps most important for practical applications, the mechanism reproduces the reported extents of Hg(o) oxidation on a single catalyst for four coals that generated HCl concentrations from 8 to 241 ppm, which covers the entire range encountered in the U.S. utility industry. Similar performance is also demonstrated for full-scale SCRs with diverse coal types and operating conditions.     

Fe-Mn基分子筛催化剂NH3低温选择性催化还原NO性能

采用柠檬酸法制备了不同Fe和Mn含量的Fe-Mn/HBeta催化剂,采用BET、XRD、SEM和XPS等方法对不同催化剂的特征参数进行表征,以氨气为还原剂,在空速为5 000 h-1的条件下,考察了活性成分负载量和焙烧温度对其活性的影响;探讨了催化剂的抗水抗硫性能.研究结果表明,焙烧温度为550℃、6%Fe-6%Mn/HBeta催化剂具有相对较优的催化活性,反应温度为90~230℃时,NO转化率为63.9%~96.99%,比表面积、孔体积和平均孔径分别为356.19 m2/g、0.61 cm3/g和16.83 nm,活性成分在催化剂表面高度分散,催化剂表面Mn主要以Mn3+和Mn4+存在,且以Mn4+居多;反应温度为180℃条件下,6%Fe-6%Mn/HBeta催化剂具有较好的抗水能力和同时抗水抗SO2能力,但单独抗SO2能力较差.     

Effect of CO on NO oxidation over platinum based catalysts for hybrid fast SCR process

The oxidation characteristics of NO over Pt/TiO2 (anatase, rutile) catalysts have been determined in a fixed bed reactor as a function of O2, CO and SO2 concentrations in the presence of 8% water. The conversion of NO to NO2 increases with increasing O2 concentration up to 12% and it levels off. This saturation effect is more pronounced over rutile-Pt/TiO2 (r-Pt/TiO2) than that of anatase-Pt/TiO2 (a-Pt/TiO2). The presence of CO increases NO oxidation significantly and this enhanced effect is more pronounced on a-Pt/TiO2 than that on r-Pt/TiO2 with increasing CO concentration at lower temperatures. The same effect is also observed on the catalysts with different Pt and tungsten oxide (WO3) loadings. With increasing Pt and WO3 loadings on TiO2 support (Pt-WO3/TiO2), formation of NO2 is high even at lower temperatures. The presence of SO2 significantly suppresses the oxidation of NO over both r-Pt/TiO2 and a-Pt/TiO2 catalysts but it is less pronounced due to low stability of sulfate on a-Pt/TiO2.     

钾对催化剂选择性催化还原氮氧化物的性能影响特性研究

试验就碱金属钾对两种催化剂V2O5/TiO2(VT)和V2O5/TiO2-SiO2(VTS)选择性催化还原(SCR)氮氧化物的性能影响作了相关研究.运用BET比表面积、X射线衍射(XRD)谱图、傅立叶变换透射红外光谱(FT-IR)谱图对催化剂进行表征.结果表明,试验制备的TiO2-SiO2比表面积达360 m2/g,催化剂表面活性组分高度分散;NH3吸附红外谱图显示催化剂VTS具有丰富的表面酸;催化剂抗钾毒害试验发现,钾易与B酸位结合从而降低对NH3的吸附量和吸附活性,催化刺VTS具有明显优于VT的抗钾毒害性能.归因于部分钾优先与VTS表面酸结合,从而降低对钒活性物种的毒害.此外,失活程度跟钾/钒(K/V)的摩尔比密切相关.催化活性随反应进行不断降低,且24 h内难以恢复到原有水平.     

Mn/GO复合催化剂催化氧化NO

针对尾气中NO浓度高且传统方法脱除NO代价高的问题,研究了锰固载氧化石墨诱导单过硫酸氢钾(PMS)催化氧化并吸收NO方法。通过浸渍法在氧化石墨上负载了Mn3O4制得Mn/GO催化剂,以此为催化剂催化PMS氧化NO。研究了pH、PMS投加量、催化剂投加量以及温度等因素对NO氧化率的影响。结果表明,该系列Mn/GO催化剂可以有效地诱导PMS氧化NO,热处理时间为7 h时催化效果最佳。同时,对Mn/GO(7 h)的FT-IR、XRD、SEM、EDS以及XPS表征可知,Mn3O4是主要的锰氧化物,并成功负载在GO表面。     

The effects of manganese precursors on Mn-based/TiO2 catalysts for catalytic reduction of NO with NH3

Manganese acetate (MnAc) and manganese nitrate (MnN) were employed as precursors for the preparation of MnAc)/TiO2, Mn (N)/TiO2, Mn(Ac)-Ce/TiO2, and Mn(N)-Ce/TiO2 by impregnation. These complexes were used as catalysts in the low-temperature selective catalytic reduction of NO with NH3. The influence of manganese precursors on catalyst characteristics, the reduction activity, and the stability of the catalysts to poisoning by H2O and SO2 were studied. Experiments showed that Mn(N) produced MnO2 with large grain sizes in Mn(N)/TiO2 catalyst. On the contrary, Mn(Ac) led to highly dispersed and amorphous Mn2O3 in Mn (Ac)/TiO2 catalyst, which had better catalytic activity and stability to SO2 at low temperatures. The doping of cerium reduced the differences in catalytic performance between the catalysts derived from different Mn precursors.     

Natural manganese ore catalyst for low-temperature selective catalytic reduction of NO with NH3 in coke-oven flue gas

Environmental Science and Pollution Research - Different types of manganese ore raw materials were prepared for use as catalysts, and the effects of different manganese ore raw materials and...     

Effect of the Mn oxidation state and lattice oxygen in Mn-based TiO2 catalysts on the low-temperature selective catalytic reduction of NO by NH3

TiO₂-supported manganese oxide catalysts formed using different calcination temperatures were prepared by using the wet-impregnation method and were investigated for their activity in the low-temperature selective catalytic reduction (SCR) of NO by NH₃ with respect to the Mn valence and lattice oxygen behavior. The surface and bulk properties of these catalysts were examined using Brunauer-Emmett-Teller (BET) surface area, X-ray diffraction (XRD), temperature-programmed reduction (TPR), and temperature-programmed desorption (TPD). Catalysts prepared using lower calcination temperatures, which contained Mn⁴⁺, displayed high SCR activity at low temperatures and possessed several acid sites and active oxygen. The TPD analysis determined that the Brönsted and Lewis acid sites in the Mn/TiO₂ catalysts were important for the low-temperature SCR at 80～160 and 200～350 °C, respectively. In addition, the available lattice oxygen was important for attaining high NO to NO₂ oxidation at low temperatures.

Implications: Recently, various Mn catalysts have been evaluated as SCR catalysts. However, there have been no studies on the relationship of adsorption and desorption properties and behavior of lattice oxygen according to the valence state for manganese oxides (MnO_x). Therefore, in this study, the catalysts were prepared by the wet-impregnation method at different calcination temperatures in order to show the difference of manganese oxidation state. These catalysts were then characterized using various physicochemical techniques, including BET, XRD, TPR, and TPD, to understand the structure, oxidation state, redox properties, and adsorption and desorption properties of the Mn/TiO₂ catalysts.     

改性电石渣干法催化净化工业废气中的NO

采用电石水解制取乙炔气体后的废渣(电石渣)脱除工业废气中的NO。结果表明：通过KOH改性之后,该电石渣NO脱除效果有显著提高;改性电石渣NO脱除率随反应温度的升高呈先增大后减小的趋势。正交实验结果显示,各因素对NO脱除率的影响顺序大小为：浸渍浓度>焙烧温度>焙烧时间。NO脱除率随着KOH浓度增加呈现先增加后下降的趋势,随着焙烧温度和焙烧时间的增加NO脱除率下降;当KOH浓度为5 mol.L⁻¹,焙烧温度为300 ℃,焙烧时间为2 h时,改性电石渣的NO脱除率可达80.66%。表征分析结果表明,改性电石渣微观结构明显发生改变,可为催化NO反应提供反应场所,生成的K₂CO₃为NO的去除提供了更多活性点位。     

Mn/USY分子筛催化剂低温SCR脱硝性能

以USY分子筛为载体,采用等体积浸渍法制备了不同Mn负载量的Mn/USY催化剂。借助BET、XRD、SEM和FT-IR等手段,考察了催化剂的物相结构及脱硝活性。在90~210 ℃温度范围内,随着反应温度的升高,NO转化率逐渐提高,脱硝效率在210 ℃达到50%以上,其中10 Mn/USY的NO转化率高于其他几组催化剂。通过SEM和BET结果可以看出,Mn/USY分子筛催化剂的比表面积随着Mn负载量的增加而减少。新鲜的催化剂颗粒分散均匀,呈松散的堆叠状态,H2O和SO2实验后催化剂分散程度降低,比表面积、孔径和孔体积都有所下降。XRD结果表明,10 Mn/USY催化剂中MnO2的晶体特征峰最为明显,除此之外没有发现其他Mn或MnOx衍射峰。FT-IR分析结果表明金属Mn的负载并未对USY分子筛的内部结构造成破坏。     

Research status,challenges and future prospects of renewable synthetic fuel catalysts for CO2 photocatalytic reduction conversion

Environmental Science and Pollution Research - In recent years, with global climate change, the utilization of carbon dioxide as a resource has become an important goal of human society to achieve...     

Modification of photocatalytic property of BaTiO3 perovskite structure by Fe2O3 nanoparticles for CO2 reduction in gas phase

In this work, perovskite structure of BaTiO₃ was coupled with Fe₂O₃ in different molar ratios achieving the best photocatalytic performance of CO₂ reduction in the presence of CH₄ as reducing agent; both of them are main greenhouse gases. The photocatalysts were synthesized by facile hydrothermal method. The samples were characterized by XRD, FTIR, FESEM, EDX, UV–Vis DRS, and photoluminescence (PL) analyses. The BaTiO₃ synthesized in this research showed a weak PL signal which is due to the intrinsic ferroelectric property as has been observed in previous reports. Compared to the pure BaTiO₃ and Fe₂O₃, the heterojunctions exhibited enhanced photocatalytic activity. The maximum CO₂ reduction under visible light irradiation was obtained to be 22% during 60 min process time. The enhanced photocatalytic activity could be attributed to the increased optical absorption, the good separation, and immigration of photogenerated charge carriers that decreased the recombination rate of charge carriers in the n–n heterojunction.

     

等离子体-催化协同处理挥发性有机物的催化剂研究进展

等离子体与催化技术的结合解决了单一用等离子体时的能量利用率、产率低及应用条件高的缺陷.总结了不同等离子体-催化协同作用的催化剂催化活性;在此基础上探讨了催化剂的组成、表面性质和结构对其催化活性的影响以及催化剂使用过程中的稳定性,分析了等离子体催化协同处理挥发性有机物(VOCs)过程中的反应机制;最后,对催化剂存在的问题和今后的研究方向进行了探讨.     

Ce-Fe/ACF催化剂低温选择性催化还原NO的研究

以ACF作为载体制备了一系列不同质量分数的CeO2和Fe2O3混合负载型催化剂,研究了它们催化净化NO的低温活性和活性的稳定性。同时,对比研究了CeO2/ACF和Ce-Fe/ACF净化NO的能力。活性实验结果表明,催化剂中加入Fe2O3作为助催化,能使催化剂活性、稳定性等得到明显改善。反应温度为80~120℃时,比相同质量分数CeO2/ACF催化剂的NO脱除效率提高幅度最大达到18.11%,增幅度较大;随着反应温度的升高,催化剂的脱硝效率提高幅度趋小,反应温度为200℃时,两者相比,NO脱除效率仅提高1.98%;而后随着温度的攀升,催化剂的脱硝效率提高幅度又慢慢趋大,且其效率平稳。