Cerium-tungsten oxides supported on activated red mud for the selective catalytic reduction of NO_(x)

Activated red mud(RM)has been proved to be a promising base material for the selective catalysis reduction(SCR)of NOx.The inherent low reducibility and acidity limited its low-temperature activity.In this work,molybdenum oxide,tungsten oxide,and cerium oxide were used to reconfigure the redox sites and acid sites of red mud based catalyst.When activated red mud was reconfigured by cerium-tungsten oxide(Ce-W@RM),the NOx conversion kept above 90%at 219-480℃.The existence of Ce^(3+)/Ce^(4+) redox electron pairs provided more surface adsorbed oxygen(O_(α)) and served as a redox cycle.Positive interactions between Ce,W species and Fe oxide in red mud occurred,which led to the formation of unsaturated chemical bond and promoted the activation of adsorbed NH_(3) species.WO_(3) and Ce_(2)(WO_(4))_(3)(formed by solid-state reaction between Ce and W species)could provide more Brønsted acid sites(W-O modes of WO_(3),W=O or W-O-W modes of Ce_(2)(WO_(4))_(3)).CeO_(2) species could provide more Lewis acid sites.The Langmuir-Hinshelwood(L-H)routes and Eley-Rideal(E-R)routes occurred in the low-temperature SCR reaction on the Ce-W@RM surface.NH_(4)^(+) species on Brønsted acid sites,NH_(3) species on Lewis acid sites,bidentate nitrate and bridging nitrate species were key active intermediates species.

One-pot synthesis of bimetallic CeCu-SAPO-34 for high-efficiency selective catalytic reduction of nitrogen oxides with NH_(3) at low temperature

NH_(3) selective catalytic reduction(SCR) has been widely recognized as a promising technique for reducing nitrogen oxides from diesel vehicle exhausts. High-efficiency SCR catalysts that could perform at low temperatures are essential to denitration. In this work, a series of bimetallic CeCu-SAPO-34 molecular sieves were synthesized by one-step hydrothermal method. The Ce Cu-SAPO-34 maintained good crystallinity and a regular hexahedron appearance of Cu-SAPO-34 after introducing Ce species, while exhibiting a higher specific surface area and pore volume. The as-prepared CeCu-SAPO-34 with 0.02%(mass) Ce constituent exhibited the best catalytic activity below 300℃ and a maximum NO_(x) conversion of 99% was attained;the NO_(x) removal rates of more than 68% and 94% were achieved at 150℃ and 200℃, respectively. And the introduction of cerium species in Cu-SAPO-34 improves the low-temperature hydrothermal stability of the catalyst towards NH_(3)-SCR reaction. Additionally, the introduced Ce species could enhance the formation of abundant weak Br?nsted acid centers and promote the synergistic effect between CuO grains and isolated Cu^(2+) to enhance the redox cycle, which benefit the NH_(3)-SCR reaction.This work provides a facile synthesis method of high-efficiency SCR denitration catalysts towards diesel vehicles exhaust treatment under low temperature.

Research progress in the SO2 resistance of the catalysts for selective catalytic reduction of NOx

The selective catalytic reduction （SCR） of NOx with NH3 has been proven to be an efficient technology for NOx conversion to N2. However, the catalysts used for SCR usually suffer from the problem of sulfur poisoning which seriously limits their practical application. This review summarized sulfur poisoning mechanisms of various SCR deNG catalysts and strategies to reduce deactivation caused by SO2 such as doping metals, controlling the structures and morphologies of the catalysts, and selecting appropriate supports. The methods and procedures of catalysts preparation and the reaction conditions also have effect on SO2-resistance of the catalysts. Several novel catalyst systems that exhibited good SO2 resistance are also introduced. This paper could provide guidance for the development of highly efficient sulfur-tolerant deNOx catalysts.

Influence of coke rate on thermal treatment of waste selective catalytic reduction(SCR)catalyst during iron ore sintering

Waste selective catalytic reduction(SCR)catalyst as a hazardous waste has a significant impact on the environment and human health.In present study,a novel technology for thermal treatment of waste SCR catalyst was proposed by adding it to sinter mix for iron ore sintering.The influences of coke rate on the flame front propagation,sinter microstructure,and sinter quality during sintering co-processing the waste SCR catalyst process were studied.In situ tests results indicated the maximum sintering bed temperature increased at higher coke rate,indicating more liquid phase generated and higher airflow resistance.The sintering time was longer and the calculated flame front speed dropped at higher coke rate.Sinter microstructure results found the coalescence and reshaping of bubbles were more fully with increasing coke rate.The porosity dropped from 35.28%to 25.66%,the pore average diameter of large pores decreased from 383.76μm to 311.43μm.With increasing coke rate,the sinter indexes of tumbler index,productivity,and yield,increased from 33.2%,9.2 t·m^(-2)·d^(-1),28.9%to 58.0%,36.0 t·m^(-2)·d^(-1),68.9%,respectively.Finally,a comprehensive index was introduced to systematically assess the influence of coke rate on sinter quality,which rose from 100 to 200 when coke rate was increased from 3.5%(mass)to 5.5%(mass).

Kinetics of selective catalytic reduction of NO by NH_3 on Fe-Mo/ZSM-5 catalyst

The catalyst of Fe-Mo/ZSM-5 has been found to be more active than Fe-ZSM-5 and Mo/ZSM-5 separately for selective catalytic reduction （SCR） of nitric oxide （NO） with NH3. The kinetics of the SCR reaction in the presence of O2 was studied in this work. The results showed that the observed reaction orders were 0.74-0.99, 0.01-0.13, and 0 for NO, O2 and NH3 at 350-450℃, respectively. And the apparent activation energy of the SCR was 65 kJ/mol on the Fe-Mo/ZSM-5 catalyst. The SCR mechanism was also deduced. Adsorbed NO species can react directly with adsorbed ammonia species on the active sites to form N2 and H2O. Gaseous O2 might serve as a reoxidizing agent for the active sites that have undergone reduction in the SCR process. It is also important to note that a certain amount of NO was decomposed directly over the Fe-Mo/ZSM-5 catalyst in the absence of NH3.

Plasma-catalytic Selective Reduction of NO with C_(2)H_(4)in the Presence of Excess Oxygen

This paper reports observations of significant synergistic effects between dielectric barrier discharge (DBD) plasmas and Cu-ZSM-5 catalysts for C2H4 selective reduction of NOx at 250 °C in the presence of excess oxygen by using a one-stage plasma-over-catalyst (POC) reactor. With the reactant gas mixture of 530 ppm NO, 650 ppm C2H4, 5.8% O2 in N2 and GHSV = 12000 h-1, the pure catalytic, pure plasma-induced (discharges over fused silica pellets) and plasma- catalytic (in the POC reactor) NOx conversion are 39%, 1.5% and 79%, respectively. The in-situ optical emission spectra of the reactive systems imply some short-lived active species formed from plasma-induced and plasma-catalytic processes may be responsible to the observed synergistic effects in this one-stage POC system.

Catalytic Performance of MnO_x-WO_3/TiO_2 Catalyst for Selective Catalytic Reduction of NO_x with NH_3 and Its Tolerance Towards SO_2

The performance of Mn-W/TiO2 for selective catalytic reduction（SCR） of NOx with NH3 and its resistance to different concentrations of SO2 at various temperatures were investigated. The results show that WO3 increased the active sites and enhanced the strength of acid, so it was an effective promoter of MnOJTiO2. The NOx conversion on Mn-W/TiO2 ranges from 80.3% to 99.6% between 100 ℃to 350℃ at GHSV=18900 h 1, while N2 product selectivity changes from 100% to 98.7%. In the presence of 0.01% SO2 and 6% H20, NOx conversion maintained 98.5% at 120℃. The influence of more than 0.01% SO2 on the activity of MnOx-WO3/TiO2 will disappear if the temperature rises above 250℃. By means of heating and sweeping with He, the activity of the catalysts can be recovered. At 300℃, NOx conversion yielded 99% with 0.07% SO2 and reached the level of commercial V-W/TiO2 catalysts. The Mn-W/TiO2 catalyst showed excellent performance for SCR of NOx with NH3 in a wider range of temperature with strong tolerance to SO2.

Selective catalytic NO_x reduction on Antimony promoted V_2O_5-Sb/TiO_2 catalyst

Quantum chemical calculation was carried out to choose a promoter which can reduce the poisoning of V2O5/TiO2 catalysts by SO2. Several atoms were chosen as candidates and new catalysts were synthesized by impregnation method. The NOx conversion rate was measured at temperatures between 100 and 400 ℃ and poisoning effect was investigated. The most promising candidate promoter, Se, was excluded because of its high vapor pressure. On the other hand, Sb shows best promoting properties. Sb promoted catalyst reaches the maximum NOx conversion rate at 250 ℃. It also shows considerably enhanced resistance to poisoning of V2O5/TiO2 catalysts by SO2.

Selective catalytic reduction of NO with NH_3 over sol-gel-derived CuO-CeO_2-MnO_x/γ-Al_2O_3 catalysts

Granular CuO-CeO2-MnOx/γ-Al2O3 catalysts were synthesized by the sol-gel method. The performance of the CuO-CeO2-MnOx/γ-Al2O3 catalysts for the selective catalytic reduction (SCR) was studied in a fixed bed system. Preliminary tests were carried out to analyze the behavior of NH3 and NO over catalyst in the presence of oxygen. The optimum temperature range for SCR over the CuO-CeO2-MnOx/γ-Al2O3 catalysts is 300-400 ℃ . The catalysts maintain nearly 100% NO conversion at 350 ℃. The NH3 oxidation experiments show that both NO and N2O are produced gradually with the increase of temperature. The catalysts in this experiment have a stronger oxidation property on NH3, which improves the denitrification activity at low temperature. The over-oxidation of NH3 at high temperature is the main cause leading to a decrease in the NO conversion. The NH3 and NO desorption experiments show that NH3 and NO can be adsorbed on CuO-CeO2-MnOx/γ-Al2O3 granular catalysts. The transient response of NH3 and NO indicates that the SCR reaction proceeds in accordance with the Eley-Rideal mechanism. The adsorbed NO has little influence on the denitrification activity in SCR process.

Cu改性MIL-100(Fe)催化剂的SCR-C_(3)H_(6)脱硝特性

烃类化合物选择性催化还原氮氧化物(SCR-HC)是一种很有发展前景的脱硝技术。催化剂有效的氧化-还原能力是影响其活性的关键因素。利用水热法制备了新型有机金属骨架MIL-100(Fe),通过超声浸渍法合成不同Cu含量的m Cu-MIL-100(Fe)催化剂,在固定床微反应器中对其催化C_(3)H_(6)选择性还原NO的特性进行了实验研究。结果表明Cu的引入使MIL-100(Fe)催化活性得到改善。2.3Cu-MIL-100(Fe)的NO转化率在275℃下可达到100%,275~400℃范围内可维持85%以上NO转化率及90%以上N_(2)选择性,且具有较好抗SO_(2)的能力。通过各种技术手段对催化剂的微观结构及物化性质进行了表征,并对反应机理作了进一步讨论。N_(2)吸附-脱附结果表明,加入适量Cu可以增大催化剂的比表面积,并增强催化剂表面对反应气体的吸附能力;XPS研究结果表明,Cu可以提高催化剂表面的氧空位数目。Cu与Fe之间具有协同作用,二者之间存在电子转移现象。H_(2)-TPR曲线表明Cu使催化剂的还原特征峰向低温方向移动,增强了其还原性能。

基于7状态船舶柴油机SCR脱硝系统的精细化建模与控制

传统的3状态选择性催化还原(SCR)脱硝模型只关注NO和NH3对系统的影响,忽略了NO2的作用,但研究发现,NO2的影响也不可忽视。为此,考虑NO和NO2对SCR脱硝系统的影响,设计面向双催化剂、包含NO2的7状态船舶SCR脱硝系统机理模型,分析NO2对船舶脱硝系统性能的影响,讨论精细化模型的精度。此外,从节能降耗角度出发,设计模型预测控制器,对比不同模型的控制效果,结果表明,相比于传统的3状态模型,基于7状态的精细化模型具有更优的控制效果。

SCR脱硝系统在危废焚烧烟气处理中的应用研究

选择性催化还原(Selective Catalytic Reduction,SCR)是危废焚烧企业广泛应用的烟气处理工艺。某危废焚烧处置项目SCR脱硝系统位于烟气处理的湿法脱酸工艺后端,SCR反应器设计温度为260℃,升温过程需要消耗大量天然气加热烟气。因此,有必要优化工艺方案设计,开展经济效益分析,明确SCR脱硝系统运行风险,提出应对措施。经设计,采用两级烟气换热系统,湿法脱酸后的烟气与袋滤房出口烟气一次换热,再与SCR反应后的烟气二次换热,两次加热升温后烟气温度达到220℃,然后烟气进入SCR反应器。与天然气直接加热方式相比,该工艺可明显减少天然气消耗量,每年可节省天然气费用约530万元,具有很好的环境效益与经济效益。

基于储氨停喷响应特性的SCR系统氨泄漏识别

有效识别出氨(NH_(3))泄漏是柴油机NO_(x)转化(De NO_(x))系统实现精确闭环控制与自适应修正的基础.针对NO_(x)传感器对排气中的NH_(3)和NO_(x)存在交叉敏感这一情况,提出了一种基于停喷状态下选择性催化还原(SCR)系统储氨响应特性的NH_(3)泄漏识别方法.在工况条件合适时,持续将NO_(x)转化效率的传感器测量值和预测值的比值与标定限值进行对比,超过限值时则触发停喷诊断动作,并在停喷过程中通过对比催化器的储氨消耗超过限值的时间与转化效率低于限值的时间先后,实现对NH_(3)泄漏状态的准确识别.结果表明:该方法能够有效识别出SCR系统的NH_(3)泄漏,并能够在NO_(x)排放超过车载故障诊断(OBD)限值时准确识别出NO_(x)排放超标.

SCR脱硝分区喷氨影响因子研究及优化

近年来,针对SCR脱硝系统过量喷氨和氨逃逸等问题,分区喷氨控制技术开始在燃煤电厂进行应用。该文采用数值模拟方法(CFD)对某600 MW机组的SCR分区喷氨系统进行流场模拟,并提出优化方案,优化后催化剂入口氨氮比和喷氨分区对应性显著改善,最后分析不同负荷工况对流场的影响。

低温SCR脱硝催化剂的研究现状与挑战

综述了贵金属、分子筛、碳基和金属氧化物SCR催化剂的研究进展,全面阐述了影响低温催化剂活性的因素,包括前驱体引入方法、制备条件、载体预处理和催化剂结构,分析了SO_(2)和/或H_(2)O导致低温SCR催化剂中毒/失活的机理及缓解方式,总结了提高SCR催化剂抗毒化能力的方法并指出了未来研究的发展方向。

A Comparison of Hydrothermal Aging, SO2 and Propene Poisoning Effects on NH3-SCR over Cu-ZSM-5 and Cu-SAPO-34 Catalysts

This study was aimed to investigate the effects of hydrothermal aging, propene and SO2 poisoning on the ammonia-selective catalytic reduction (NH3-SCR) performance of both Cu-SAPO-34 and Cu-ZSM-5. The catalytic activities of fresh, aged and poisoned samples were tested in ammonia-selective catalytic reduction (NH3-SCR) of NOx conditions. The XRD, TG and N2-desorption results showed that the structures of the Cu-SAPO-34 and Cu-ZSM-5 remained intact after 750˚C hydrothermally aged, SO2 and propene poisoned. After hydrothermal aging at 750˚C for 12 h, the NO reduction performance of Cu-ZSM-5 was significantly reduced at lower temperatures, while that of Cu-SAPO-34 was less affected. Moreover, Cu-SAPO-34 catalyst showed high NO conversion with SO2 or propene compared to Cu-ZSM-5. However, Cu-ZSM-5 showed a larger drop in catalytic activity with SO2 or propene compared to Cu-SAPO-34 catalyst. The H2-TPR results showed that Cu2 ions could be reduced to Cu and Cu0 for Cu-ZSM-5, while no significant transformation of copper species was observed for Cu-SAPO-34. Meanwhile, the UV-vis DRS results showed that CuO species were formed in Cu-ZSM-5, while little changes were observed for the Cu-SAPO-34. Cu-SAPO-34 showed high sulfur and hydrocarbon poison resistance compared to Cu-ZSM-5. In summary, Cu-SAPO-34 with small-pore zeolite showed higher hydrothermal stability and better hydrocarbon and sulfur poison resistant than Cu-ZSM-5 with medium-pore.

Density functional theory(DFT) studies of vanadium-titanium based selective catalytic reduction(SCR) catalysts

Based on density functional theory(DFT)and basic structure models,the chemical reactions on the surface of vanadium-titanium based selective catalytic reduction(SCR)denitrification catalysts were summarized.Reasonable structural models(non-periodic and periodic structural models)are the basis of density functional calculations.A periodic structure model was more appropriate to represent the catalyst surface,and its theoretical calculation results were more comparable with the experimental results than a nonperiodic model.It is generally believed that the SCR mechanism where NH3 and NO react to produce N2 and H2 O follows an Eley-Rideal type mechanism.NH2 NO was found to be an important intermediate in the SCR reaction,with multiple production routes.Simultaneously,the effects of H2 O,SO2 and metal on SCR catalysts were also summarized.

CeO2/TiO2 Monolith Catalyst for the Selective Catalytic Reduction of NOx with NH3： Influence of H2O and SO2

The influences of H2O and SO2 on CeO2/TiO2 monolith catalyst for the selective catalytic reduction（SCR） of NOx with NH3 were investigated. In the absence of SO2, H2O inhibited the SCR activity, which might be ascribed to the competitive adsorption of H2O and reactants such as NH3 and/or NOx. SO2 could promote the SCR activity of CeO2/TiO2 monolith catalyst in the absence of H20, while in the presence of H20 it speeded the deactivation. During the SCR reaction in SO2-containing gases, Ce（Ⅲ） sulfate species formed on the catalyst surface, resulting in the en- hancement of Bronsted acidity. This played a significant role in the enhanced SCR activity. However, in the presence of both H2O and SO2, a large amount of ammonium-sulfate salts formed on the catalyst surface, which resulted in the blocking of catalyst pores and deactivated the catalyst. In addition, the NOx conversion was more sensitive to gas hourly space velocity in the presence of H20 than in the absence of H20. The relatively high space velocity would result in a higher formation rate of ammonium-sulfate salts on per unit catalyst in the presence of H2O and SO2, which caused obvious deactivation of Ce/TiO2 monolith catalyst.

NTP辅助SCR降低柴油机NOX排放的机理研究

为了研究低温等离子体在低温条件下辅助SCR降低柴油机NOX排放过程中的作用机理,设计搭建了NTP-NH3-SCR复合系统。在实验过程中,利用3个气体分析仪对NTP,NH3-SCR系统、NTP-NH3-SCR复合系统的净化效率进行独立测算,得到了3种净化系统对NOX净化效率随温度变化的曲线。结果显示,在低于250℃的低温条件下,SCR对NOX的净化效率较低,但在NTP的辅助下,能把NOX净化效率从不高于40%提高到60%以上,且温度越低,NTP的加入对SCR降低柴油机NOX的净化效率提高越明显。根据电晕放电理论,分析了NOX流经NTP时产生的物理化学变化,结果表明,在低温工况下,NTP预氧化NO对SCR减少柴油机NOX排放量有较大的促进作用。

满足超低NOx排放标准的紧凑耦合SCR系统控制策略研究

紧凑耦合选择性催化还原(ccSCR)技术是满足加州超低NOx排放标准的一种切实可行的后处理技术,本文通过数值仿真计算的方法对ccSCR系统控制策略进行研究。利用SCR单状态模型对催化器NH3存储、NOx排放和NH3泄漏进行预测,分析了未安装ccSCR催化器时美国联邦测试循环(FTP)NOx排放特性,基于此提出了双喷嘴独立控制策略和双喷嘴联合控制策略。研究结果表明,ccSCR系统可以充分利用尾气热量,大大缩短尿素起喷时间,FTP循环冷起动尿素起喷时间从568降低到51 s。双喷嘴联合控制策略将ccSCR催化器和下游SCR催化器中的NH3存储进行联合控制,采用该策略的ccSCR系统NOx转化效率达到99.56%,NOx比排放满足未来加州超低NOx排放法规要求。