添加WO3提高铈锆固溶体的氨选择性催化还原NOx反应活性

采用程序升温氨脱附、程序升温还原和X射线光电子能谱分析手段表征了加入WO3前后CeO2-ZrO2颗粒催化剂的表面性能变化.结果表明,WO3一方面增加了催化剂的酸性,另一方面略微提高了催化剂的氧化还原性能.在氨选择性催化还原氮氧化物反应中,当NH3/NO=1,空速为90000h-1的条件下,CeO2-ZrO2催化剂上氮氧化物转化率低于65%,而10%WO3/CeO2-ZrO2催化剂催化活性大于80%,所对应的温度区间为220～420℃.通入10%CO2和10%H2O后,由于竞争吸附,CeO2-ZrO2催化剂上的氮氧化物转化率低于46%,而10%WO3/CeO2-ZrO2催化剂上的氮氧化物转化率大于80%的温度区间移至230～500℃.     

新型铬锰复合氧化物低温选择性催化氨还原NOx

采用柠檬酸法合成了一系列铬锰复合氧化物催化剂,利用X射线衍射及X射线光电子能谱研究了催化剂活性相态,并考察了铬锰摩尔比对反应活性的影响. 结果表明,该体系在有氧条件下氨低温选择性催化还原氮氧化物反应中显示出优异的活性,其中Cr(0.4)-MnOx催化剂具有最佳低温催化活性,在空速 30 000 h-1和120 ℃条件下, NOx转化率达98.5%, N2选择性达100%. 在MnOx中添加Cr后形成了CrMn1.5O4晶相, 该相态在低温选择性催化还原NOx过程中起重要作用.     

Low Temperature Catalytic Hydrolysis of Carbon Disulfide on Activated Carbon Fibers Modified by Non-thermal Plasma

In order to improve the carbon disulfide (CS₂) catalytic hydrolysis efficiency of activated carbon fibers (ACFs), ACFs surface was modified by non-thermal plasma (NTP). In particular, the effects of modification conditions on the catalyst properties were studied, including the reactor structure, modification atmosphere, modification time, output voltage and discharge gap. The catalytic activity study showed that ACFs with NTP modification enhanced CS₂ catalytic hydrolysis. The optimal reactor structure, modification atmosphere, modification time, output voltage and discharge gap was a coaxial cylinder, an N₂ atmosphere, 5 min, 7 kV and 7.5 mm, respectively. The effect of the NTP modification on the micro-structural properties of the ACFs was characterized using scanning electron microscopy (SEM), Brunauer–Emmett–Teller (BET) and X-ray photoelectron spectroscopy (XPS) methods. The results showed that NTP modification improved the dispersion of functional groups and increased the number of oxygen-containing and nitrogen-containing functional groups, thus the catalytic activity could be enhanced. The present results indicated that NTP modification was an effective way to manipulate ACFs surface properties for the CS₂ catalytic hydrolysis reaction.     

低温等离子体协同Ag/Al2O3选择性催化丙烯还原氮氧化物反应的原位红外光谱研究

 研究了稀燃条件下低温等离子体(NTP)协同丙烯在Ag/Al2O3催化剂上选择性催化还原NOx反应,通过原位漫反射傅里叶变换红外光谱(DRIFTS)对NTP协同前后反应气中NO和C3H6的吸附以及丙烯选择性催化还原反应进行了表征. 结果表明,丙烯的活化是Ag/Al2O3上选择性催化还原反应的关键步骤. NTP活化反应气体后, Ag/Al2O3表面-NCO、R-NO2和有机酸根等物种的数量大幅度增加,并且其催化还原NOx的低温(＜350 ℃)活性也显著提高. 在NTP协同前后,选择性催化还原过程可能存在两条反应路径,较低温度下主要是-NCO 生成N2, 而较高温度下则是-CN向N2转化.     

Enhanced Catalytic Activity and SO2/H2O Tolerance for Selective Catalytic Reduction of NOx with NH3 over Titanate Nanotubes Supported MnOx–CeO2 Catalyst at Low Temperature

Catalysis Surveys from Asia - An environment-friendly selective catalytic reduction (SCR) catalyst with high catalytic activity and strong anti-poisoning performance at low temperature is strongly...     

Pt/SAPO-34在低温H2选择催化还原NO反应中的催化活性

考察了贫燃条件下Pt/SAPO-34催化剂低温(60～260℃)选择催化还原(H2-SCR)消除NO的催化性能,研究了载体、金属负载量和反应条件对催化性能的影响.结果表明,0.5%Pt/SAPO-34催化剂的活性高于相同金属负载量的Pt/SiO2和Pt/ZSM-5,其在高空速(80000h-1)时的最高NO转化率可达78.8%,N2选择性为75.2%,而在空速降低到10000h-1时,其NO转化率可达到100%.通过原外漫反射红外光谱初步研究了H2-SCR反应的机理,发现反应的中间物种主要是-NO3-.     

BiMnO_3钙钛石上低温NH_3选择性催化还原NO

首次将钙钛石BiMnO3用于低温条件下NH3选择性催化还原NO反应中.结果表明,该催化剂在100～240oC范围内表现出较好的催化活性.实验和理论计算显示,相对于LaMnO3,BiMnO3优异的低温催化活性归因于其较强的Lewis酸性和较多的表面吸附氧物种.此外,BiMnO3还具有较好的抗水、抗硫性能.     

富氧条件下Ag/Al2O3和Cu/Al2O3组合催化剂催化C3H6选择性还原Nox的性能

 在全自动催化剂活性评价装置上,考察了富氧条件下Ag/Al2O3和Cu/Al2O3两种催化剂上催化丙烯还原NOx的活性. 在实验温度范围(200～650 ℃)内,Ag/Al2O3具有 优异的催化丙烯选择性还原NOx的活性,但同时有大量副产物CO形成. Cu/Al2O3选择性催化丙烯还原NOx的活性不高,却能有效促进CO的氧化. 在无水条件,Ag/Al2O3-Cu/Al2O3组合体系具有与Ag/Al2O3相似的脱除NOx活性,同时使CO在300 ℃以后几乎完全转化. 在10%水蒸气存在的情况下,Ag/Al2O3-Cu/Al2O3组合催化剂脱除NOx的活性下降,但水蒸气对CO转化率的影响不大.     

新型MnOx催化剂用于低温NH3选择性催化还原NOx

 首次采用低温固相法制备了无载体MnOx催化剂并将其用于NOx的低温NH3选择性催化还原. 该催化剂为晶化度极低的混合锰氧化物,部分为粒径40～60 nm的棒状晶体颗粒,其余是更细小的无定形颗粒; 催化剂的BET比表面积为150.8 m2/g, 吸附能力较强, NOx吸附量可达138.27 μmol/g. 在模拟尾气试验条件下, MnOx催化剂的低温活性很高, 80 ℃时NOx转化率即可达到98.25%; 反应产物N2选择性高于96.6%; 当通入0.01%SO2和10%H2O后,由于竞争吸附导致NOx转化率有所下降,但仍可保持在70%左右,且不利影响在停止添加SO2和H2O后逐渐消失.     

氢气对Ag/Al2O3和Cu/Al2O3催化剂选择性催化C3H6还原Nox反应的影响

 添加H2对Ag/Al2O3和Cu/Al2O3催化剂选择性催化C3H6还原NOx反应具有不同的影响. 原位漫反射红外光谱分析表明,在Ag/Al2O3催化剂上, H2的存在促进了C3H6部分氧化产物烯醇式物种(RCH=CH-O-)和乙酸盐等的形成,烯醇式物种和硝酸盐为主要反应中间体,二者间的相互反应性能很强,能形成高浓度的反应关键中间体异氰酸酯(-NCO)表面吸附物种,因此NOx的去除活性提高; 而在Cu/Al2O3催化剂上, H2的存在并没有促进C3H6部分氧化产物的形成,而且抑制了硝酸盐的形成,进而抑制了C3H6部分氧化产物与硝酸盐反应形成表面-NCO 物种,导致NOx的去除活性降低.     

Performance and Kinetics Studies on Selective Catalytic Reduction of NOx with NH3 over MnOx-WO3/TiO2 Catalyst

The catalytic activities of MnOx-WO3/TiO2 for selective catalytic reduction(SCR) of NO with NH3 were investigated in a wide range of temperature and reaction condition.It yielded a NOx conversion of 80.3%-99.6% and a N2 product selectivity of 100%-98.7% during 100 °C to 350 °C at gas hourly space velocity(GHSV)=18900 h-1.In the presence of 0.01% SO2 and 6% H2O at 120 °C,the NOx conversion can maintain 98.5%.At 300 °C and with 0.07% SO2 in reactant stream,the NOx conversion stabilized at 99% as high as the commercial V-W/TiO2 catalyst's level.The steady-state kinetics study shows that O2 played a promoting role.In the presence of less than 1.5% O2,NOx conversion can increase sharply with the increase of O2 concentration.The reaction order was zero with respect to NH3 and first with respect to NO with excess O2 and H2O.The kinetics active energy(Ea) of Mn-W/TiO2 was calculated to be 6.24 kJ/mol according to the kinetic experiment at various temperatures,much lower than those of other catalysts reported in the literature.Mn-W/TiO2 is an excellent catalyst for SCR of NO with NH3 by now.     

Pd基催化剂上H2快速选择催化还原 NOx

 首次研究了 Pd 基催化剂上氢快速选择催化还原 NOx 反应 (快速 H2-SCR 反应). 结果表明, Pd/Al2O3 和 Pd/SiO2 催化剂表现出极高的活性, 在 200 oC 以上时 NOx 转化率可达 100%; 但 Pd/MgO 催化剂在整个考察温度范围均没有活性, 这表明载体对催化剂快速 H2-SCR 活性有决定性作用. 与常规 H2-SCR 反应相比, 快速 H2-SCR 反应明显提高了 NOx 的消除效率. 原位漫反射红外光谱结果表明, 快速 H2-SCR 反应活性的提高来源于加速生成的氨物种以及后续反应速率的加快.     

载体酸性对铜基交联黏土催化剂上C3H6选择性催化还原NO反应的影响

采用聚合羟基复合阳离子合成交联蒙脱土Al-Ce-PILC, 并分别用NH4NO3和(NH4)2SO4处理后， 将其作为载体, 采用浸渍法制备了应用于C3H6选择性催化还原NO反应的铜基交联黏土催化剂Cu/Al-Ce-PILC. 用Py-IR， IR和DSC等表征技术研究了不同处理方式对Al-Ce-PILC的结构、 酸性和催化剂活性的影响. 结果表明, 未经处理的Al-Ce-PILC中同时存在L酸和B酸, 以L酸为主, Cu/Al-Ce-PILC上NO的最大转化率仅为18。5％; 用NH4NO3处理提高了L酸量, NO转化率降低; 而用(NH4)2SO4处理改变了Al-Ce-PILC的酸性结构, 增大了B酸量, 并形成了超强酸中心, 催化剂上NO转化率显著提高, 在350 ℃时达最大值50.2％. B酸对于Cu/Al-Ce-PILC上NO的还原是必要的, 它有利于C3H6吸附并适度氧化为活性中间物种, 其酸量和酸强度的增加是催化剂活性改善的主要原因.     

Mechanism of the Selective Catalytic Reduction of NOx with NH3 over W-Doped Fe/TiO2 Catalyst

The W-doped Fe/TiO2 catalyst prepared by an impregnation method exhibited a good NH3-selective cata- lytic reduction（SCR） activity and N2 selectivity with broad operation temperature window. The interaction between Fe and W could increase the amount of surface chemisorbed oxygen, and thus enhances the low temperature SCR activity by facilitating the fast SCR of 2NH3＋NO＋NO2 →2N2＋3H2O. The NH3-SCR reaction mechanism over the W-Fe/TiO2 was fully investigated via in situ diffuse reflectance infrared Fourier transform spectroscopy（in situ DRIFTS）. In the low temperature range（〈250 ℃）, the reactive surface species were mainly coordinated NH3, ionic NH~ and adsorbed NO2 species, and the SCR mainly followed the Langmuir-Hinshelwood mechanism, during which the adsorbed NO2 species became the important active sites. In the high temperature range（〉250 ℃）, the reactive surface species were mainly NH2, and the SCR mainly followed the Eley-Rideal mechanism, during which the for- mation of NH2NO intermediate species after H-abstraction of NH3 was the rate-determining step.     

等离子体与催化剂协同催化CH4选择性还原脱硝反应

研究了在低温等离子体和催化剂共同作用下,CH4选择催化还原(SCR)NO的反应.在所考察的金属氧化物催化剂中,γ-Al2O3表现出最高的催化活性.当等离子体放电功率为4.5 W,反应温度为300℃时,NO转化率为56.5％;该条件下单纯等离子体反应和以γ-Al2O3为催化剂时NO转化率分别为28.9％和0,表明等离子体...     

CeO2 Nanoparticle-Loaded MnO2 Nanoflowers for Selective Catalytic Reduction of NOx with NH3 at Low Temperatures

CeO₂ nanoparticle-loaded MnO₂ nanoflowers, prepared by a hydrothermal method followed by an adsorption-calcination technique, were utilized for selective catalytic reduction (SCR) of NO_x with NH₃ at low temperatures. The effects of Ce/Mn ratio and thermal calcination temperature on the NH₃–SCR activity of the CeO₂-MnO₂ nanocomposites were studied comprehensively. The as-prepared CeO₂-MnO₂ catalysts show high NO_x reduction efficiency in the temperature range of 150–300 °C, with a complete NO_x conversion at 200 °C for the optimal sample. The excellent NH₃–SCR performance could be ascribed to high surface area, intimate contact, and strong synergistic interaction between CeO₂ nanoparticles and MnO₂ nanoflowers of the well-designed composite catalyst. The in situ diffuse reflectance infrared Fourier transform spectroscopy (DRIFTs) characterizations evidence that the SCR reaction on the surface of the CeO₂-MnO₂ nanocomposites mainly follows the Langmuir–Hinshelwood (L-H) mechanism. Our work provides useful guidance for the development of composite oxide-based low temperature NH₃–SCR catalysts.     

富氧条件下Ag/Al2O3-Cu/Al2O3组合催化剂催化乙醇选择性还原NOx

 在富氧条件下,以乙醇为还原剂,考察了不同金属负载量的Ag/Al2O3和Cu/Al2O3催化剂选择性还原NOx的活性. 结果表明,4%Ag/Al2O3和10%Cu/Al2O3分别为各自体系中的最佳催化剂. 4%Ag/Al2O3具有很高的选择性催化还原NOx的活性,但同时会产生一定量的副产物CO. 10%Cu/Al2O3选择性催化还原NOx的活性不高,但却具有很好的消除CO的活性. 将4%Ag/Al2O3和10%Cu/Al2O3以不同方式组合,其评价结果表明,4%Ag/Al2O3-10%Cu/Al2O3组合催化剂具有与单纯4%Ag/Al2O3相似的NOx脱除活性,同时能够完全消除反应过程中产生的CO,并且能大大降低尾气中乙醇和乙醛的浓度.     

DRIFT Study on Cr2O3-SO42-/TiO2 Catalyst for Low Temperature Selective Catalytic Reduction of NO with NH3

Chromium oxides supported on TiO2 showed good activity for the selective catalytic reduction of NO by NH3.The catalytic activity of Cr2O3-SO42-/TiO2 catalyst was greatly enhanced by the addition of SO42-into TiO2 support.The catalyst surface properties were characterized with NH3-TPD（temperature programmed desorption） and H2-TPR（temperature programmed reduction）.The sulphate on the catalyst surface could enhance the acidity and redox of the catalyst obviously.The reaction mechanism on this catalyst was researched in detail by in situ diffuse reflectance Fourier transform infrared（FTIR） spectroscope.Eley-Rideal and Langmuir-Hinshelwood mechanism existed simultaneously for selective catalytic reduction（SCR） reaction of NO over Cr2O3-SO42-/TiO2 catalyst.     

一种新的甲烷低温燃烧催化剂Au—Pt／Co3O4

考察了Pt和Pd的引入对Au/Co3O4催化剂的甲烷燃烧活性的影响,发现在Au/Co3O4（Au的质量分数为2%-5%）催化剂中掺入少量的Pt(如0.2%）,可使甲烷的催化燃烧活性得到显著的提高;相对于Au/Co3O4催化剂,其甲烷的最低全转化温度降低了50℃。便Pd的引入未提高甲烷燃烧的活性。表明Au-Pt/Co3O4是一个很有应用潜力的甲烷低温燃烧催化剂。     

Cu-SAPO-18催化剂氨选择性催化还原NOx钾中毒机理的研究

研究了不同水热老化温度对钾(K)中毒0.4K-Cu-SAPO-18样品的结构及其NH₃-SCR(NH₃作为还原剂的选择性还原技术)催化活性的影响. 结果表明, K中毒对样品结构影响较小, 但明显降低了其NH₃-SCR性能, 在350 ℃ 时, K中毒样品0.4K-Cu-SAPO-18的NO转化率为65.88%, 明显低于未中毒Cu-SAPO-18样品的90.85%. 水热老化温度明显影响催化剂的结构, 减少了活性位点, 降低了表面酸性. 随着水热老化温度升高, 催化剂的AEI结构被破坏, 活性物种数量降低, 催化活性明显下降. 氢气程序升温还原 (H₂-TPR)结果表明, 孤立的Cu²⁺和Cu⁺的总量分别从未中毒Cu-SAPO-18样品的66.61和1.32 μmol/g变化到K中毒0.4K-Cu-SAPO-18样品的39.52和101.96 μmol/g, 表明K中毒样品中孤立Cu²⁺ 容易转化为Cu₂O. K中毒后, 样品的弱酸、 中强酸、 强酸性位点的数量降低, 分别从未中毒Cu-SAPO-18样品的0.201, 0.103和0.302 mmol/g降低到中毒0.4K-Cu-SAPO-18样品的0.102, 0.086和0.071 mmol/g. 氨气程序升温脱附(NH₃-TPD)和原位红外结果表明, K竞争性地取代了催化剂中孤立的Cu²⁺和H⁺, 使K中毒0.4K-Cu-SAPO-18样品的活性位和酸性位减少, 导致催化活性下降. 在低温 NH₃-SCR反应中, K中毒和未中毒样品均以Eley-Rideal(E-R)和Langmuir-Hinshelwood(L-H)机理进行, 而L-H机理占主导地位, 但K中毒样品的反应速率明显降低.