燃煤电厂砷中毒SCR脱硝催化剂的失活特性研究

分别对某燃煤电厂运行了3个月和3年的SCR脱硝催化剂进行活性测试,并结合X射线原子荧光(XRF)、氢气程序升温还原(H_2-TPR)、比表面积(BET)和X射线光电子能谱(XPS)等对催化剂进行分析,探究SCR脱硝催化剂的砷中毒失活特性。结果表明,在富砷煤的使用条件下,电厂运行3个月和3年的催化剂都已发生严重失活,活性下降主要是由砷中毒引起,而且主要发生在催化剂表层,其中运行3个月催化剂活性下降主要由砷的物理中毒引起的,而对于运行3年的催化剂,由砷引起的物理中毒和化学中毒共同导致催化剂脱硝效率下降。     

660MW燃煤电厂商用SCR催化剂的失活与再生

以某660 MW燃煤电厂运行30000 h的商用SCR脱硝催化剂为实验对象,在新鲜催化剂为参照下,结合SEM、BET、NH_3-TPD、XRF和XPS等表征方法,考察了商用SCR脱硝催化剂失活原因和硫酸清洗再生效果。结果表明:运行30000 h的SCR脱硝催化剂失活的主要原因是碱金属(K和Na)、砷和硫酸盐在催化剂表面沉积,堵塞了催化剂的微孔,降低了催化剂比表面积,并且碱金属、砷等与催化剂表面酸性活性位点反应,降低了催化剂表面的酸性强度。运行30000 h的SCR脱硝催化剂经过稀硫酸再生后,350°C脱硝性能由42.62%提升到78.30%。酸洗再生能有效脱除催化剂表面的碱金属,对砷和硫酸盐也有一定脱除作用,并有利于SCR脱硝催化剂表面酸性强度增加,化学吸附氧含量比例提升,这些均能提高SCR脱硝催化剂脱硝活性。     

燃煤电厂砷中毒SCR脱硝催化剂的失活特性研究

分别对某燃煤电厂运行了3个月和3年的SCR脱硝催化剂进行活性测试,并结合X射线原子荧光(XRF)、氢气程序升温还原(H_2-TPR)、比表面积(BET)和X射线光电子能谱(XPS)等对催化剂进行分析,探究SCR脱硝催化剂的砷中毒失活特性。结果表明,在富砷煤的使用条件下,电厂运行3个月和3年的催化剂都已发生严重失活,活性下降主要是由砷中毒引起,而且主要发生在催化剂表层,其中运行3个月催化剂活性下降主要由砷的物理中毒引起的,而对于运行3年的催化剂,由砷引起的物理中毒和化学中毒共同导致催化剂脱硝效率下降。     

垃圾焚烧脱硝催化剂钙镁失活与活性恢复特性

以国内某垃圾焚烧电厂失活选择性催化还原(SCR)脱硝催化剂为研究对象,针对Ca、Mg失活因素进行失活特性研究,同时探讨垃圾焚烧失活催化剂的活性恢复方法与原理。对新催化剂、失活催化剂和再生催化剂样品进行脱硝性能对比测试。利用扫描电子显微镜(SEM)、N₂吸附-脱附和X射线荧光光谱(XRF)表征催化剂样品的表面结构和化学组成;进行X射线光电子能谱(XPS)和傅里叶变换红外光谱(FTIR)测试,分析失活和再生催化剂的化学形态变化;采用NH₃程序升温脱附(NH₃-TPD)和H₂程序升温还原(H₂-TPR)研究催化剂的酸性位点变化和氧化还原特性。结果表明,由于受到Ca、Mg等失活因素的影响,失活催化剂脱硝性能大幅下降,300～350℃温度区间内的脱硝效率从新催化剂的95%以上下降到80%左右;利用“EDTA清洗+活性物质负载”方法再生后的催化剂脱硝能力明显恢复,RegCat样品在300～350℃温度区间的脱硝效率可恢复至新催化剂水平。Ca、Mg在催化剂表面形成性质稳定的硫酸盐,同时消耗大...     

SCR脱硝催化剂的失活与再生

根据环境保护部公告2014年第5号文《废烟气脱硝催化剂危险废物经营许可证审查指南》国家鼓励废催化剂优先再生。本文介绍了电厂选择性脱硝(SCR)催化剂的失活原因,失活催化剂的吹灰除尘、清洗、活性附着、干燥煅烧的活性再生的工艺方法。保证其满足行业标准催化剂的要求。     

SCR脱硝催化剂失活再生

介绍火电机组SCR脱硝催化剂在运行过程中失活的原因,以及再生的技术方法,包括水洗再生、化学清洗再生以及活性液浸渍再生。     

常规失活SCR催化剂制备的低温脱硝催化剂在玻璃窑炉上的应用研究

选择性催化还原技术(SCR)是国内外运用最多也是最为成熟的脱除氮氧化物的技术,而SCR脱硝催化剂是其核心所在。由于烟气中有K、Na、SO_2等物质,使用中烟气通过催化剂,随着时间累积,以上物质会导致催化剂中毒、失活。失活后的催化剂需进行如填埋、处置等,污染环境、浪费资源。以常规失活的SCR催化剂为载体,植入低温脱硝活性物质V_2O_5及掺杂Mn、Co、Ce、Fe和Cu制备了低温脱硝催化剂,并检测了植入前后低温催化剂的化学成分,评价了催化剂脱硝性能及抗水、抗碱、抗砷能力。结果表明:制备的低温脱硝催化剂脱硝效率高,抗水抗碱抗砷能力强。在某日用玻璃窑炉上应用后,脱硝效率超过89.3%,达到了设计要求。     

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。     

选择催化还原(SCR)反应机理研究进展

简述了NH₃和NO在催化剂表面吸附、转化活化和反应历程及H₂O和SO₂对以上反应行为的影响。分析表明,NH₃氧化脱氢进而与NO反应是决定NH₃反应性和最终产物的关键。NO以气态（Eley-Rideal机理）或硝基类物质等吸附态（Langmuir-Hinshelwood机理）形式参与选择催化还原（SCR）反应。提高催化剂酸性和氧化还原循环性能,利于NH₃和NO吸附和转化及相互间反应。高温时,H₂O影响轻微,而SO₂增强催化剂酸性,提高脱硝活性。低温时,H₂O和SO₂抑制NO吸附和转化活化,导致硫铵盐累积和活性位转变为硫酸盐使催化剂失活。因此,提高抗H₂O、抗SO₂性能是低温脱硝催化剂研发的重要方向。而发展在线升温等再生工艺以解决硝酸盐或含硫化合物导致的失活问题,对保障低温脱硝系统长期稳定运行具有重要意义。     

SCR脱硝催化剂再生清洗液的制备和应用

在现代工业生产应用中,选择性催化还原法(Selective Catalytic Reduction,SCR)烟气脱硝技术是应用最为普遍的方法,而脱硝催化剂作为整个SCR脱硝系统的重要组分,其催化活性的高低能够直接刺激到最后的脱硝效率~([1])。然而在实际的应用生产中,催化剂运行过程中会因为热烧结、磨损、堵塞、中毒等原因而使得活性降低甚至失活~([2-4]),因此运行3-5年就需要对其进行改换。且催化剂生产费用高昂,随意丢弃会对环境产生很大的损害。因此,利用制备脱硝催化剂再生清洗液的方法对催化剂进行再生清洗是非常有必要的~([2])。本文实施水洗再生的方法通过配制催化剂清洗液对活性较低或已经失活的催化剂进行清洗,再通过配制好的孔径修复液对催化剂进行孔径修复,最终得出再生清洗液对可再生的失活催化剂的再生效果显著,为工业上催化剂活性恢复提供了指导根据和实践基础。     

Revisiting the concepts of competition between reaction and diffusion in poisoned catalysts

The competition between diffusion and first‐order irreversible reaction in poisoned catalysts is revisited. Two cases are considered for isothermal slab catalysts: uniform and shell‐progressive (or pore‐mouth) poisoning. Analytical concentration profiles are derived, and the implications on catalyst performance are evaluated in different regimes (chemical‐ or diffusion‐controlled) for different levels of poisoning. It was found that depending on the poisoning mechanism, the activity decay can be more or less pronounced. Being of particular concern is the pore‐mouth poisoning at high Thiele modulus, conditions under which catalyst performance is drastically affected. The reagent concentration profiles allowed the explanation of the phenomena occurring at the particle scale, in particular the effectiveness factors, observed reaction rates, and poisoning factors' dependence on the Thiele modulus and fraction of the poisoned catalyst; it was found that such relationships are dependent on the mechanism of deactivation. © 2012 Canadian Society for Chemical Engineering     

凹凸棒石低温SCR脱硝催化剂的研究进展

选择性催化还原（SCR）脱硝技术是目前主流的氮氧化物脱除技术,其核心是催化剂。凹凸棒石成本低廉,性能优越,适合用作SCR催化剂的载体,而且以凹凸棒石为载体的催化剂显示出良好的低温选择性和稳定性,具有很好的应用前景。本文总结了凹凸棒石低温SCR脱硝催化剂的研究进展,阐述了活性组分、制备方法、前体物种、活性组分负载量、煅烧温度、元素掺杂等因素对催化剂脱硝活性的影响,同时简要介绍了导致此类催化剂失活的原因以及失活催化剂的再生方法,并指出在凹凸棒石负载型低温脱硝催化剂上进行的SCR脱硝反应遵循E-R机理,最后指出此类催化剂的未来研究方向主要是进一步提高现有催化剂的低温催化活性和抗中毒能力,实现工业化应用。     

钒钛基SCR脱硝催化剂碱土金属中毒

分别制备了钒钨体系和钒钼体系的新鲜催化剂,并通过浸渍法、固态扩散法与干混法分别制备了碱土金属中毒的催化剂,比较了中毒方法、碱土金属以及催化助剂种类等因素对催化剂脱硝活性的影响,并利用程序升温脱附（NH₃-TPD）、程序升温还原（H₂-TPR）和X射线光电子能谱分析（XPS）等表征手段进行分析。结果表明,3种中毒方法中,浸渍法碱土金属中毒对催化剂毒害作用最大;Ca对催化剂的毒性大于Mg,且钒钼体系催化剂比钒钨体系催化剂具有更强的抗碱土金属中毒性能。碱土金属的存在会降低催化剂表面的总酸量与酸位点的强度,提高催化剂的还原温度,改变活性组分的价态并降低催化剂上表面活性氧的比例。     

Z409/Z405G催化剂在制氢装置上的失活及再生

介绍胜利炼油厂第二制氢装置z409／Z405G轻油蒸汽转化催化剂中毒失活及再生过程。分析失活原因，提出改进措施；对催化剂进行成功再生后，z409／Z405G催化剂的活性完全恢复到中毒前的水平。     

Kinetic modeling of Fe‐BEA as NH3‐SCR catalyst—effect of phosphorous

The focus of this work is to investigate whether a previously developed microkinetic deactivation model for hydrothermally treated Fe‐BEA as NH₃‐SCR catalyst can be applied to describe chemical deactivation of Fe‐BEA due to phosphorous exposure. The model describes the experiments well for Fe‐BEA before and after phosphorous exposure by decreasing the site density, representing deactivation of sites due to formation of metaphosphates blocking the active iron sites, while the kinetic parameters are kept constant. Furthermore, the results show that the activity for low‐temperature selective catalytic reduction (SCR) is very sensitive to loss of active monomeric iron species due to phosphorous poisoning compared to high‐temperature SCR. Finally, the ammonia inhibition simulations show that exposure to phosphorous may affect the internal transport of ammonia between ammonia storage sites buffering the active iron sites, which results in a lower SCR performance during transient conditions. © 2014 American Institute of Chemical Engineers AIChE J, 61: 215–223, 2015     

烟气脱硝催化剂中毒机制与再生技术

随着烟气脱硝系统在火电厂的应用,对选择性催化还原催化剂的中毒机理和再生工艺的研究受到广泛关注。本文系统综述了脱硝催化剂的物理及化学中毒机制、再生方法及工艺。在中毒机制方面,将不同中毒机制归为三类:颗粒物或生成盐沉积在催化剂表面,堵塞催化剂通道和孔道;毒物与活性中心作用使表面的酸性性能和氧化还原性能降低;催化剂结构破坏和发生不可逆相变。在催化剂的再生方面,本文详细介绍了失活催化剂的再生工艺流程和再生液的选择,比较了不同再生技术的针对性和优缺点,最后介绍了电厂高钙项目的再生工业示范,其再生催化剂的相对活性恢复到原来的0.96,SO₂氧化率为1.0%,且各项指标达到了新鲜催化剂的水平。本文对延长催化剂使用寿命和制定废弃催化剂再生工艺具有重要指导意义。     

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.     

复合氧化物催化剂在汽车尾气净化中硫中毒及抗硫中毒机理——TPD研究

复合氧化物催化剂在汽车尾气净化中硫中毒及抗硫中毒机理——ＴＰＤ研究秦正龙杨汉培（徐州师范学院化学系，徐州２２１００９）（清江石油化工厂，淮阴２２３００２）关键词：复合氧化物催化剂汽车尾气净化ＳＯ２中毒１前言传统的汽车催化剂均以贵金属为活性组元，虽然具...     

Surface chemical characterization of deactivated low-level mercury catalysts for acetylene hydrochlorination

Mercury-containing catalysts are widely used for acetylene hydrochlorination in China. Surface chemical characteristics of the fresh low-level mercury catalysts and spent low-level mercury catalysts were compared using multiple characterization methods. Pore blockage and active site coverage caused by chlorine-containing organics are responsible for catalyst deactivation. The reactions of chloroethylene and acetylene with chlorine free radical can generate chlorine-containing organic species. SiO₂ and functional groups on activated carbon contribute to the generation of carbon deposition. No significant reduction in the total content of mercury was observed after catalyst deactivation, while there was mercury loss locally. The irreversible loss of HgCl₂ caused by volatilization, reduction and poisoning of elements S and P also can lead to catalyst deactivation. Si, Al, Ca and Fe oxides are scattered on the activated carbon. Active components are still uniformly absorbed on activated carbon after catalyst deactivation.     

Chemical deactivation of V2O5/WO3–TiO2 SCR catalysts by additives and impurities from fuels, lubrication oils and urea solution: Part II. Characterization study of the effect of alkali and alkaline earth metals

A characterization study on a practice-oriented V₂O₅/WO₃–TiO₂ SCR catalyst deactivated by Ca and K, respectively, was carried out using NH₃-TPD, DRIFT spectroscopy, and XPS as well as theoretical DFT calculations. It was found from NH₃-TPD experiments that strongly basic elements like K or Ca drastically affect the acidity of the catalysts. Detailed DRIFT spectroscopy experiments revealed that these poisoning agents mostly interact with the Brønsted acid sites of the V₂O₅ active phase, thus affecting the NH₃ adsorption. Moreover, these experiments also indicated that the V⁵⁺ = O sites are much less reactive on the poisoned catalysts. XPS investigations of the O 1s binding energies showed that the oxygen atoms of the V⁵⁺ = O sites are affected by the presence of the poisoning agents. Based on these results and on DFT calculations with model clusters of the vanadia surface, the poisoning mechanism is explained by the stabilization of the non atomic holes of the (0 1 0) V₂O₅ phase as a result of the deactivation element. Consequently, V–OH Brønsted acid sites and V⁵⁺ = O sites are inhibited, which are both of crucial importance in the SCR process. The deactivation model also gives an explanation to the very low concentrations of potassium needed to deactivate the SCR catalyst, since one metal atom sitting on such a non-atomic hole site deactivates up to four active vanadium centers.