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.

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.

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.

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.

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。

Synergetic catalysis of ceria and titania for selective reduction of NO

The promotional effect of the interaction between titania and ceria on the catalytic performance for selective reduction of NO was studied.The catalysts,CeO 2,TiO 2,CeO 2 /TiO 2 and Ti x Ce 1-x O 2,were synthesized and tested in NH 3-Selective catalytic reduction（SCR） of NO,and the samples were characterized by the Brunaller,Emmett and Teller（BET absorbed gas N 2）,X-ray diffraction（XRD）,high resolution transmission electron microscopy（HR-TEM）,and temperature programmed desorption（TPD NH 3） techniques.The improvement mechanism of the interaction between the titania and ceria had been explored and discussed from two aspects of micro-structure and surface acidity.The interaction between the titania and ceria greatly improved the catalytic activity but had little effect on the active temperature.It was first reported that the acid amount determined the catalytic activity and the acid strength determined the active temperature for NH 3-SCR of NO.

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.

SCR催化剂的组成对其脱硝性能的影响

在以TiO2为载体的基础上,考察了活性组分WO3和V2O5的质量分数以及SiO2和Al2O3的加入对SCR催化剂脱硝性能的影响,筛选出的最佳催化剂组成与某商业催化剂的催化活性、制备方法和催化剂组成进行比较。结果表明,SiO2和Al2O3的加入会降低催化剂的脱硝性能,筛选出的最佳催化剂组成为0.5%V2O5~10%WO3/TiO2;与实验室通过溶胶-凝胶法制备载体然后负载活性组分的制备方法不同,商业催化剂是将粒径均匀的锐钛矿型TiO2与玻璃纤维(主要成分为SiO2和Al2O3)通过黏合剂混合制备成型的催化剂载体,然后负载活性组分;由于制备方法和催化剂组成等方面的较大差异,0.5%V2O5~10%WO3/TiO2在低于603 K时具有很好的NO脱除率,而商业催化剂在实际烟气温度(603 K^663 K)范围内,能稳定保持90%以上脱硝率。

钒钛基SCR催化剂中毒及再生研究进展

在烟气脱硝系统中,选择性催化还原催化剂的中毒和再生是广泛关注的问题。文章介绍了钒钛基催化剂的碱金属中毒、碱土金属中毒、砷中毒和二氧化硫中毒,探讨其成因,并对中毒机理进行了分析,同时研究了避免催化剂中毒的措施以及中毒催化剂的再生技术。对碱金属中毒和碱土金属中毒催化剂的水洗再生和硫酸酸洗再生方法进行了实验评价。文章对溶胶凝胶法制备的以陶瓷颗粒为骨架的纳米负载型催化剂V2O5-WO3/TiO2(C)进行研究。实验结果表明,硫酸酸洗再生对碱金属和碱土金属中毒催化剂具有较好的再生效果。在380～410℃温度范围内可使中毒催化剂的NO去除率恢复至90%以上。水洗再生对碱金属中毒催化剂无明显效果,而在380～410℃温度范围内可使碱土金属中毒催化剂的NO去除率达到80%以上。对V2O5-WO3/TiO2(C)抗SO2性能研究表明,以锐钛TiO2为载体的V2O5-WO3/TiO2(C)催化剂具有较好的抗SO2效果。

柴油机Urea-SCR系统数值模拟与混合器结构优化

采用计算流体力学和化学反应动力学相结合的方法，运用FIRE软件对某尿素选择性还原Utea—SCR催化器系统进行全尺寸模拟，研究分析了催化器的流场及尿素液滴和组分浓度的分布规律。未加SCR混合器前，催化剂内部还原剂分布均匀性较差，NOx转化效率仅为45％～60％。最后模拟了安装挡板式和叶片式混合器的SCR系统。研究结果表明：两种混合器都可以大幅改善SCR催化剂入口还原剂的均匀性，安装混合器后，NOx转化效率提高约30％，达到85％以上。经过分析对比，叶片式混合器在改善还原剂均匀性和减少压力损失方面优于挡板式混合器。

SCR尿素结晶风险的评估与预测

在尿素结晶机理分析的基础上,提出以壁面温度的结晶容许最小碰壁量为阈值的结晶风险判定方法,建立尿素液滴碰壁量与结晶之间的关系.通过测量尿素液滴碰壁区域的排气管内外壁面温度变化过程,以结晶响应来表征尿素结晶风险.该方法通过某重型柴油机的尿素结晶过程的模拟计算和试验分析,在不同稳态工况下的结晶程度,取得较好的预测一致性.在此基础上,进一步引入结晶时间尺度辅助筛选瞬态试验循环的结晶工况窗口.提出的结晶风险评估与预测方法在实际应用中能显著缩短试验周期,节约试验验证成本.

尿素SCR-NO_x催化器流动、还原剂喷雾及表面化学反应三维数值模拟

采用计算流体动力学(CFD)耦合化学反应动力学的方法,建立了尿素水溶液喷射、热解以及催化剂表面化学反应整个尾气后处理过程的柴油机SCR-NOx催化器三维数值模型,在验证还原剂喷雾模型的基础上,对一实际柴油机SCR-NOx全尺寸催化器进行了全过程的三维数值模拟,给出了催化器的流场、温度场和浓度场的分布规律,并研究不同发动机负荷下催化器性能的变化,数值模拟计算的结果与发动机台架试验结果取得了较好的吻合。研究结果对指导柴油机SCR催化器的设计有参考价值。

NH_3-SCR工艺中硫酸铵盐的生成与分解机理研究进展

以氨为还原剂的选择性催化还原(NH_3-SCR)脱硝法具有脱硝效率高、选择性好和技术完善等优点,是目前应用最广泛的燃煤电厂等行业的烟气脱硝技术。然而,烟气中的SO_2流经SCR催化剂时,在V_2O_5的催化作用下部分氧化为SO_3,随后与NH_3和水蒸气反应生成硫酸氢铵和硫酸铵。当烟气温度低于硫酸铵盐的凝结温度时,会沉积在催化剂、空预器及其附属设备上,引发诸多严重的问题。本文首先介绍了硫酸铵盐的形成机理,随后从反应物浓度和反应温度等角度概括了影响硫酸铵盐生成的因素,分析了硫酸铵盐的沉积及其所带来的危害。然后介绍了硫酸铵盐的分解机理,重点分析了催化剂与硫酸氢铵之间的相互作用,指出了这种相互作用对硫酸氢铵分解的影响,由此提出了控制硫酸铵盐生成的措施。最后指出,系统研究NH_3-SCR工艺中硫酸铵盐的生成与分解机理将为催化剂的失活与再生、低温SCR催化剂的开发和燃煤机组等相关设备的设计和运行优化等提供理论依据。