Urea Decomposition and Implication for NOx Reduction with Cu-Zeolite and Vanadia-Selective Catalytic Reduction

Understanding urea decomposition is critical to achieve highly efficient selective catalytic reduction (SCR). The urea decomposition process in an exhaust pipe and in Cu-zeolite and vanadia-SCR (V-SCR) was studied in engine test cells. The unconverted urea at the SCR inlet can be substantial at lower temperatures. HNCO and NH₃ are two dominant products at the SCR inlet. Urea and HNCO continue to decompose in SCR catalysts, with a rate much faster than in the homogeneous stream. The HNCO hydrolysis process is extremely efficient in Cu-zeolite SCR and the abundant NH₃ from urea overdosing can improve the NO_x conversion efficiency. While for V-SCR, the HNCO hydrolysis reaction can become the rate-limiting step (especially after aging), abundant urea at low temperatures impairs NO_x reduction.     

选择性催化还原脱硝催化剂研究进展

催化剂是选择性催化还原(selective catalytic reduction,SCR)脱硝技术的核心,催化剂的低温活性、选择性和稳定性直接影响到NOx的脱除效果.SCR脱硝催化剂性能主要取决于催化剂活性组分和催化剂载体.简述了以氨、尿素和碳氢化合物等不同物质作为SCR还原剂的化学反应原理;介绍了以贵金属(Pt,Pd,Rh,Au等)和金属氧化物(V2O5,WO3,FeaO3,CuO,CrOx,MnO2.MoO3和NiO等)为催化剂活性组分.以分子筛、柱撑黏土、碳基材料和TiO2等为催化剂载体的SCR脱硝催化剂的研究进展.以V2O3为主要活性组分,以TiO2为载体的钒钛类催化剂因其理想的综合性能,目前已商业化应用.纳米有序结构TiO2薄膜可望成为理想的SCR脱硝催化荆新型载体.     

Analysis of the Coupling of HC–SCR by Ethanol and NH3–SCR on Real Engine Emissions

Selective catalytic reduction by ethanol on silver-based catalysts was proved to be very effective to abate the nitrogen oxides emitted at the exhaust of an automotive engine. Moreover, the selectivity to ammonia of this reaction may be exploited to further enhance the NOx reduction using a dedicated transition metal exchanged zeolite catalyst. This coupling between HC– and NH₃–SCR is called Dual SCR. In order to control the silver-based catalyst efficiency via ethanol injection, a NOx sensor is located downstream of it, as usually done for urea–SCR on series vehicles. Furthermore, based on the cross-sensitivity of this NOx sensor, large amounts of ammonia were estimated that would help to reduce the remaining NOx on the zeolite based catalyst. However, when measured by FTIR technique, the concentrations of ammonia produced by the HC–SCR catalyst were surprisingly not as high as expected, while large amounts of acetaldehyde were detected and, in a lesser extent, formaldehyde and hydrogen cyanide. NOx were partly reduced over the iron-exchanged zeolite catalyst, improving the overall deNOx efficiency by up to 15 points, while acetaldehyde to formaldehyde ratio reversed and ammonia concentration remains unchanged. The cross-sensitivity of the NOx sensor was further investigated on synthetic gas bench. If its partial dependence on the ammonia concentration is rather well known, the influence of aldehydes and hydrogen cyanide in presence of ammonia had not yet been investigated. The NOx sensor’s signal remains unchanged whatever the aldehydes concentration and a strong sensitivity to the hydrogen cyanide was highlighted.     

V2O5-MoO3/TiO2 催化剂的NOx选择性催化还原及SO2氧化活性

采用浸渍法以TiO₂为载体制备V₂O₅-MoO₃/TiO₂ 选择性催化还原催化剂,研究V₂O₅和MoO₃负载量对于催化剂选择性催化还原反应及SO₂氧化活性的影响,并考察氧含量、氨氮物质的量比和反应空速对3%V₂O₅-6%MoO₃/TiO₂催化剂选择性催化还原脱硝活性的影响。结果表明,随着催化剂中V₂O₅负载质量分数增加,V₂O₅-MoO₃/TiO₂ 催化剂的选择性催化还原活性和SO₂氧化活性均呈上升趋势。MoO₃的负载对催化剂的SO₂氧化活性有明显抑制作用。MoO₃负载质量分数超过9%,制备的催化剂既保持较高的低温选择性催化还原活性,又使选择性催化还原反应中的SO₂转化率小于1%。     

TiO2载体低温催化剂脱氮技术应用试验

将TiO2载体低温催化剂在水泥窑脱氮上进行了初步试验。首先取氨氮比为0.9,计算出理论喷氨量并运用于该试验。在相同烟气量和喷氨量下,经过催化反应,NOx浓度从初始的503mg/m3(标态)降为170℃时的57.5mg/m3(标态)。当喷入过量氨气时,随着温度的升高,催化剂的脱氮效率变化规律与氨气没有过量喷入时基本相同,其最大脱氮效率为89.45%,反应条件为170℃,氨气流量4.00SL/min。连续运行20h,脱氮效率上下波动为±1%。使用6个月后烟气截面催化剂孔道没有阻塞,即此低温催化剂可在水泥窑袋除尘器之后长期使用。     

Effect of the Presence of Ceria in the NSR Catalyst on the Hydrothermal Resistance and Global DeNOx Performance of Coupled LNT–SCR Systems

The global performance of coupled LNT–SCR systems, addressed to high NOx-to-N₂ conversion, minimal ammonia slip and null N₂O production, as well as the hydrothermal resistance of single NSR and SCR monolith catalysts and their coupling is discussed. Pt–Ba/Al₂O₃ and Pt–Ce–Ba/Al₂O₃ were washcoated on cordierite monoliths as NSR catalysts, and Cu/CHA was washcoated on similar monoliths as SCR catalysts. Both monoliths were coupled in two subsequent reactors to conform the LNT–SCR system. Previously to washcoating, the fresh powder catalysts and after severe hydrothermal aging were fully characterized by N₂ adsorption–desorption isotherms at 77 K, X-ray diffraction, NH₃ temperature-programmed desorption, and H₂ chemisorption to relate textural and chemical characteristics with the DeNO_x performance. The Cu/CHA catalyst shows an excellent hydrothermal resistance for the NH₃–SCR reaction. Incorporation of ceria to the model Pt–BaO/Al₂O₃is beneficial for the NO-to-NOx oxidation and NO₂ storage, improving NO conversion at low temperature and reducing the NH₃ slip. However, addition of ceria is detrimental for the hydrothermal resistance of the NSR catalyst. However, this detrimental effect is minimized when the NSR catalyst is coupled with the Cu/CHA monolith downstream of the NSR catalyst, achieving the coupled LNT–SCR device high NO conversion and minimal NH₃ slip with superior N₂ selectivity for an extended temperature windows, including as low as 220 °C, and maintaining performance even after severe hydrothermal aging.     

低温烟气脱硝催化剂制备工艺及性能探究

为了满足低温脱硝催化剂工业化的需求,对以相同组成的氧化物粉末、工业偏钛酸、水热偏钛酸为前驱体制备的脱硝催化剂的催化性能进行了考察,并利用X射线衍射、N2吸附-脱附、热重分析、机械强度等手段对催化剂的表面结构及性质进行表征分析。结果表明,随焙烧温度升高,各催化剂的活性先升高后降低,催化剂以水热偏钛酸为原料制备的催化剂(催化剂C)更适宜于工业应用,其拥有较好的低温活性、抗压强度及成型率;经过550℃焙烧10 h后催化剂的纵向抗压强度为1.06MPa,在250℃时NO转化率为97.79%。此外,对该催化剂进行脱硝活性评价及宏观动力学分析并考察了1～3 m/s气速下催化剂活性在不同烟气温度下的脱硝性能,结果表明,随气速增加催化剂的脱硝性能逐渐降低;根据Eley-Rideal机理,建立动力学方程,推算出该催化剂的反应速率常数k,并根据Arrhenius公式求得催化剂C的SCR脱硝反应活化能为32.15 kJ/mol,指前因子A为15.37×10³L/(g·min),为实际工业烟气SCR脱硝系统设计提供参考。     

中小型燃煤烟气脱硝实验研究

介绍了选用NH3作还原剂,活性炭作催化剂,在低温(<200℃)和氧气存在的条件下,选择性催化还原(SCR)NOx的技术和反应机理,研究了氧气浓度、NOx入口浓度和烟气温度对脱NOx率的影响。实验表明:当氧气体积分数为6%、烟气温度为45℃时,采用直径为8mm～9mm的圆柱体活性炭,脱NOx率最高,达92%,选择性催化还原烟气脱硝技术适宜于中小型燃煤烟气的脱硝。     

过渡金属/分子筛催化剂上选择性催化还原氮氧化物的研究进展

综述了近十年来过渡金属/分子筛催化剂上氨和碳氢化合物选择性催化还原NOx方面的研究进展。在NH3-SCR体系,着重介绍了铜基和铁基分子筛催化剂的研究状况,探讨了分子筛催化剂在该体系中的失活原因;在HC-SCR体系,总结了不同过渡金属、分子筛类型、还原剂、H2O和SO2等对催化剂活性的影响,探讨了目前比较公认的碳氢化合物选择性催化还原NOx的反应机理。最后展望了分子筛催化剂在选择性催化还原NOx领域今后的研究方向。     

低温选择性催化还原NOx的研究进展

氨选择性催化还原（NH3-SCR）是目前国内外应用最广泛的固定源脱硝技术。但由于传统的氧化钒催化剂起活温度偏高（300℃-400℃）,因此开发具有低温活性的高效脱硝催化剂成为当前国内外的研究热点。文章对近年来低温选择性催化还原法脱除Nox的研究进展进行综述。     

某燃煤电厂300MW机组SCR烟气脱硝装置结构优化

SCR烟气脱硝装置中烟气流场的分布及还原剂（NH3）与NOx的混合效果对脱硝效果起着重要作用,因此,采用数值模拟技术对于初步设计的SCR烟气脱硝装置进行结构优化是目前国内外SCR烟气脱硝装置设计必不可少的一部分。本研究采用Fluent软件对某燃煤电厂300MW机组SCR烟气脱硝装置内的烟气流动、第一层催化剂入口NH3与NOx的混合和系统压降等方面进行模拟,结果表明：BMCR工况下,结构优化后的SCR烟气脱硝装置AIG上（下）游、第一层催化剂入口和装置出口截面烟气流速相对标准偏差不超过15%;第一层催化剂入口截面NH3/NOx摩尔比相对标准偏差不超过10%;第一层催化剂入口截面烟气进入最大偏差角度处于±10°范围之间;系统压降低于800Pa。合理的设计导流板能够起到抑制弯管以及变截面所引起的流场分离现象、消除大旋流的产生使烟气更加流畅地进入催化剂等作用。     

Research progress in the SO2resistance of the catalysts for selective catalytic reduction of NOx

The selective catalytic reduction(SCR)of NOxwith NH3has 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 deNOxcatalysts and strategies to reduce deactivation caused by SO2such as doping metals,control-ling 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 SO2resistance are also introduced.This paper could provide guidance for the development of highly efficient sulfur-tolerant deNOxcatalysts.     

660MW燃煤机组SCR流场模拟优化与喷氨优化运行

以某电厂660 MW亚临界燃煤机组SCR烟气脱硝系统为研究对象,对SCR反应器内烟气流动以及喷氨分布均匀性进行数值模拟研究。通过对比首层催化剂前烟气速度分布及NH_3浓度分布,研究了SCR反应器内均流部件对烟气流场均匀特性的影响,并且在数值模拟的基础上对喷氨方式进行了优化调整研究。研究结果表明:优化调整烟道内均流部件对速度、浓度均匀性有显著改善作用;通过分析流场不均匀性得到的分区喷氨方法能够进一步优化NH_3在烟道中分布;现场试验验证了调节喷氨格栅阀门可降低SCR反应器出口NO_x浓度。本文研究可为燃煤机组SCR系统导流板优化及实际电厂喷氨优化调试提供参考。     

Control of NOx Emissions from Diesel Engine by Selective Catalytic Reduction (SCR) with Urea

Among the catalysts screened, Cu-ion exchanged ZSM5 zeolite exhibited the highest NO removal activity, particularly at low reaction temperatures below 200 °C, maintaining a wide operating temperature window. The hydrothermal stability of the CuZSM5 catalyst can be improved by the optimization of metal content of the catalyst. Through the variation of reactor operating conditions, NO conversion of better than 90% could be achieved with a minimum NH₃ slip. The decomposition of urea was also examined and a kinetic model for both thermal and catalytic decomposition of urea was developed. Urea-SCR over the CuZSM5 catalyst exhibited that the NO removal activity is competitive to that by NH₃-SCR, indicating urea can be effectively utilized in SCR reactor system as the reducing agent.     

添加Pt的选择性催化还原催化剂低温去除NOx的研究

以锐钛矿型TiO2为载体,V5O2和WO3为活性组分,添加微量贵金属Pt,制备了选择性催化还原脱硝催化剂,并对催化剂样品进行表征和脱硝性能试验.结果表明,贵金属Pt的加入,使催化剂样品比表面积、起活温度和温度窗口均发生一定的改变,在低温段具有良好的催化活性.在温度160℃和氨氮体积比0.8～1.2时,催化剂的脱硝率较稳...     

低温SCR脱硝催化剂研究进展

氮氧化物NOx(NO, NO2和N2O)是全球大气污染的主要污染物之一,引起光化学烟雾、酸雨、臭氧层破坏等环境问题,严重影响人们的生存环境和生活质量,引起了世界各国的广泛关注。针对固定源和移动源燃烧排放,各国制定了日益严格的排放标准。目前主要的脱硝技术分为选择性催化还原(SCR)、选择性非催化还原(SNCR)、氧化脱硝和活性炭吸附脱硝等。SNCR的应用有较高的条件,影响其成功运行的主要因素有温度、氨氮比、氨气在烟气中的分布和停留时间等,故SNCR的工业应用存在一定的局限性。SCR脱硝技术比其它脱硝技术应用更广泛,其中脱硝多安排于除尘脱硫后,此时温度多处于100?250℃之间。为提高SCR脱硝性能,低温SCR脱除NOx是目前研究最热门的烟气脱硝技术。本工作综述了近年来低温SCR脱硝催化剂的研究进展,介绍了锰基催化剂、钒基催化剂及碳基催化剂的发展现状,对单组分Mn基催化剂、负载型Mn基催化剂和复合型Mn基催化剂进行了综述,从V基催化剂的制备对脱销的影响和脱硝机理进行了表述,综述了过渡金属掺杂对C基催化剂的影响,阐述了烟气中H2O和SO2对催化反应的影响及低温SCR反应的脱硝机理,对低温SCR催化剂进行了总结并对其未来发展进行了展望。     

铜系低温选择性催化还原脱硝催化剂的研究进展

选择性催化还原（SCR）技术已广泛应用在燃煤电站烟气脱硝技术中,开发低温高活性、高抗中毒性能的催化剂体系已经成为国内外学者的研究重点。Cu系催化剂由于具有良好的脱硝性能及水热稳定性,得到了广泛的研究和关注。本文综述了近年来活性组分Cu负载在TiO₂、Al₂O₃、碳基材料和分子筛等材料上的研究进展;重点分析了Cu系催化剂低温SCR反应机理,主要包括Eley-Rideal （E-R）机理和Langmuir-Hinshelwood （L-H）机理,同时分析了SCR反应的两个必然过程：吸附（NH₃吸附和NO_x吸附）和反应;简要地介绍了Cu系催化剂的抗水抗硫中毒性能研究现状以及反应机理,同时介绍了碱金属中毒、飞灰和催化剂烧结对催化剂失活的影响,结合生命周期分析SCR脱硝系统还原剂氨和尿素对NO排放的影响。在此基础上展望了未来铜系催化剂的研究方向：采用新型方式对催化剂进行改性、进一步采用表征和模拟技术研究催化体系的反应机理、优化锅炉和催化剂设计减轻催化剂失活以及研究适用于其他还原剂条件的高选择性催化剂。     

水热处理和钨添加对低钒催化剂高温脱硝性能的影响

利用真空过量浸渍法在TiO₂和WO₃-TiO₂载体上负载0.5%钒（质量分数）制备了V₂O₅-TiO₂ （VTi）和V₂O₅/WO₃-TiO₂（VWTi）催化剂,并在含有10%（体积分数）水蒸气的空气氛下750℃水热处理24h得到处理态的VTi-A和VWTi-A催化剂。研究了水热老化和钨掺杂对催化剂脱硝效率的影响,并通过XRD、TEM、NH₃-TPD、H₂-TPR、XPS和Raman等表征方法对催化剂的结构和表面特性进行了表征分析。研究表明,水热处理和钨的协同作用使催化剂中产生更多的聚合态VO_x和低价态钒（V⁴⁺+V³⁺）。这两类活性物质所含有的氧物种具有较强SCR反应活性,可改善VWTi催化剂的高温脱硝性能,即使在酸性位数量减少的情况下仍有提升,这是低钒含量催化剂可满足燃气机组高温脱硝需求的主要原因。     

CeO2的添加对MnOx/ACFN催化剂脱除NOx性能影响

以经过硝酸改性后的活性炭纤维（ACFN）为载体,采用等体积浸渍法制备了MnOx/ACFN催化剂。测试了其在以氨气为还原剂的低温选择性催化还原（SCR）过程中的催化活性,并考察了活性组分MnOx的负载量、金属氧化物CeO2的复合负载方法及负载量对催化剂脱硝活性的影响。同时运用XRD和SEM对催化剂理化特性进行表征。结果表明,采用共沉淀法添加CeO2、总负载量为15%、且铈与锰的物质的量比为3∶2、反应温度为200 ℃时,催化剂的活性最高,对NOx的去除率达到92.2%。     

以偏钛酸为原料的催化剂的脱硝性能研究

以偏钛酸为原料通过浸渍法和固相物质的热分解法来制备以NH3为还原剂选择性催化还原NOx的催化剂V2O5-WO3/TiO2。着重考察催化剂组成、NH3/NO摩尔比和模拟烟气中O2浓度对催化剂脱硝性能的影响。催化剂的脱硝性能测试结果表明催化剂V2O5(1.2%)-WO3(8.8%)/TiO2具有较高的催化活性和较宽的活性温度窗口,NO的转化率最高可达98.77%。综合考虑NH3逃逸、设备腐蚀和环境问题,NH3/NO摩尔比控制在1.2以内比较合适;富氧条件对脱硝催化反应的进行更有利。