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.

Enhanced selective catalytic reduction of NO with NH3 via porous micro-spherical aggregates of Mn–Ce–Fe–Ti mixed oxide nanoparticles

We rationally designed a high performance denitration(De-NOx) catalyst based on a micrometer-sized spherical Mn–Ce–Fe–Ti(CP-SD)catalyst for selective catalytic reduction(SCR). This was prepared by a co-precipitation and spray drying(CP-SD) method. The catalyst was systematically characterized, and its morphological structure and surface properties were identified. Compare with conventional Mn–Ce–Fe–Ti(CP) catalysts, the Mn–Ce–Fe–Ti(CP-SD) catalyst had superior surface-adsorbed oxygen leading to enhanced 'fast NH3-SCR' reaction. The asobtained Mn–Ce–Fe–Ti(CP-SD) catalyst offered excellent NO conversion and N2 selectivity of 100.0% and 84.8% at 250℃, respectively, with a gas hourly space velocity(GHSV) of 40,000 h-1. The porous micro-spherical structure provides a larger surface area and more active sites to adsorb and activate the reaction gases. In addition, the uniform distribution and strong interaction of manganese, iron, cerium, and titanium oxide species improved H2O and SO2 resistance. The results showed that the Mn–Ce–Fe–Ti(CP-SD) catalyst could be used prospectively as a denitration(De-NOx) catalyst.

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.

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.

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.

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.

Transformation and removal of ammonium sulfate aerosols and ammonia slip from selective catalytic reduction in wet flue gas desulfurization system

Selective catalytic reduction(SCR) denitration may increase the emission of NH4+and NH3.The removal and transformation characteristics of ammonium sulfate aerosols and ammonia slip during the wet flue gas desulfurization(WFGD) process, as well as the effect of desulfurization parameters, were investigated in an experimental system equipped with a simulated SCR flue gas generation system and a limestone-based WFGD system.The results indicate that the ammonium sulfate aerosols and ammonia slip in the flue gas from SCR can be partly removed by slurry scrubbing, while the entrainment and evaporation of desulfurization slurry with accumulated NH4+will generate new ammoniumcontaining particles and gaseous ammonia.The ammonium-containing particles formed by desulfurization are not only derived from the entrainment of slurry droplets, but also from the re-condensation of gaseous ammonia generated by slurry evaporation.Therefore,even if the concentration of NH4+in the desulfurization slurry is quite low, a high level of NH4+was still contained in the fine particles at the outlet of the scrubber.When the accumulated NH4+in the desulfurization slurry was high enough, the WFGD system promoted the conversion of NH3 to NH4+and increased the additional emission of primary NH4+aerosols.With the decline of the liquid/gas ratio and flue gas temperature, the removal efficiency of ammonia sulfate aerosols increased, and the NH4+emitted from entrainment and evaporation of the desulfurization slurry decreased.In addition, the volatile ammonia concentration after the WFGD system was reduced with the decrease of the NH4+concentration and p H values of the slurry.

Design and operational considerations for selective catalytic reduction technologies at coal-fired boilers

By the end of 2010, China had approximately 650 GW of coal-fired electric generating capacity producing almost 75% of the country＇s total electricity generation. As a result of the heavy reliance on coal for electricity generation, emissions of air pollutants, such as nitrogen oxides （NOx）, are increasing. To address these growing emissions, the Ministry of Environmental Protection （MEP） has introduced new NOx emission control policies to encourage the installation of selective catalytic reduction （SCR） technologies on a large number of coalfired electric power plants. There is, however, limited experience with SCR in China. It is therefore useful to explore the lessons from the use of SCR technologies in other countries. This paper provides an overview of SCR technology performance at coal-fired electric power plants demonstrating emission removal rates between 65% and 92%. It also reviews the design and operational challenges that, if not addressed, can reduce the reliability, performance, and cost-effectiveness of SCR technologies. These challenges include heterogeneous flue gas conditions, catalyst degradation, ammonia slip, sulfur trioxide （SO3） formation, and fouling and corrosion of plant equipment. As China and the rest of the world work to reduce greenhouse gas emissions, carbon dioxide （CO2） emissions from parasitic load and urea-to-ammonia conversion may also become more important. If these challenges are properly addressed, SCR can reliably and effectively remove up to 90% of NOx emissions at coal-fired power plants.

N-doped graphene and TiO_2 supported manganese and cerium oxides on low-temperature selective catalytic reduction of NO_x with NH_3

A series of N-doped graphene(NG)and TiO_2 supported MnO_x–CeO_2 catalysts were prepared prepared by a hydrothermal method.The catalysts with different molar ratios of Mn/Ce(6:1,10:1,15:1)were investigated for the low-temperature selective catalytic reduction(SCR)of NO_x with NH_3.The synthesized catalysts were characterized by HRTEM,SEM,XRD,BET,XPS,and NH_3-TPD technologies.The characterization results indicated that manganese and cerium oxide particles dispersed on the surface of the TiO_2–NG support uniformly,and that manganese and cerium oxides existed in different valences on the surface of the TiO_2–NG support.At Mn element loading of 8 wt%,MnO_x–CeO_2(10:1)/TiO_2–1%NG displayed superior activity and improved SO_(2 )resistance.On the basis of the catalyst characterization,excellent catalytic performance and SO_2 tolerance at low temperature were attributed to the high content of manganese with high oxidation valence,extensive oxidation of NO into NO_2 by CeO_2 and strong NO adsorption capacity,and electron transfer of N-doped graphene.

Effects of Na+on Cu/SAPO-34 for ammonia selective catalytic reduction

Copper-exchanged chabazite（Cu/CHA） catalysts have been found to be affected by alkali metal and alkaline earth ions. However, the effects of Na＋ ions on Cu/SAPO-34 for ammonia selective catalytic reduction（NH_3-SCR） are still unclear. In order to investigate the mechanism, five samples with various Na contents were synthesized and characterized. It was observed that the introduced Na＋ ion-exchanges with H＋and Cu2＋of Cu/SAPO-34. The exchange of H＋is easier than that of isolated Cu2＋. The exchanged Cu2＋ions aggregate and form ＂CuAl_2O4-like＂ species.The NH_3-SCR activity of Cu/SAPO-34 decreases with increasing Na content, and the loss of isolated Cu2＋and acid sites is responsible for the activity loss.

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.

Effects of support acidity on the reaction mechanisms of selective catalytic reduction of NO by CH_(4) in excess oxygen

The reaction mechanisms of selective catalytic reduction(SCR)of nitric oxide(NO)by methane(CH4)over solid superacid-based catalysts were proposed and testified by DRIFTS studies on transient reaction as well as by kinetic models.Catalysts derived from different supports would lead to different reaction pathways,and the acidity of solid superacid played an important role in determining the reaction mechanisms and the catalytic activities.Higher ratios of BrØnsted acid sites to Lewis acid sites would lead to stronger oxidation of methane and then could facilitate the step of methane activation.Strong BrØnsted acid sites would not necessarily lead to better catalytic performance,however,since the active surface NO_(y) species and the corresponding reaction routes were determined by the overall acidity strength of the support.The reaction routes where NO_(2)moiety was engaged as an important intermediate involved moderate oxidation of methane,the rate of which could determine the overall activity.The reaction involving NO moiety was likely to be determined by the step of reduction of NO.Therefore,to enhance the SCR activity of solid superacid catalysts,reactions between appropriate couples of active NO_(y)species and activated hydrocarbon intermediates should be realized by modification of the support acidity.

Evaluation of Flue Gas Denitration Catalyst

Routine testing and evaluation of denitration catalyst performance are important approaches for effective operation and management of flue gas denitration system. A selective catalytic reduction (SCR) denitration catalyst used in a power plant in Xiamen was investigated in this study. The surface activity, microscopic properties and surface deposit of the catalyst were tested. It was found that: the activity (K/K 0) of the catalyst was 0.72 after 25 144 hours of operation. Almost no pores in the used catalyst had a channel diameter less than 3.5 nm. The specific surface area reduced significantly to 13.5% 17.7%. Loss of VO X compound was observed. Crystal particles showed some degree of conglomeration. Further study found that the concentrations of Ca 2+ , Na + , K + and P deposited on the surface of the used catalyst were 4.5 5, 115 140, 4.6 5.7, and 7.4 7.9 times of that on fresh catalyst, respectively. Accumulation of Arsenic (As) on the catalyst was also found. The research methods adopted in this study and the results of the experiments are useful for developing catalyst testing and evaluation program in China. They may play an important role in optimizing the operation of flue gas De-NO X system, selection of regeneration process, increase of catalyst life time, and reduction of operation cost.

水泥行业SCR中温脱硝催化剂研究进展

选择性催化还原技术(SCR)在水泥行业脱硝中被广泛应用,其中,高温范围内(280–350℃)已有较为完善的SCR技术及体系,但在中温区仍有待突破。本工作以中温脱硝催化剂为重点,综述了Mn、Ce、V系脱硝催化剂的研究进展,并分析了Sm、Nb、Ho、Sb、La、Mo、Pr的掺杂对于脱硝催化剂的改性,结合水泥窑炉烟尘中SO_(2)、H_(2)O、碱金属含量高的特点,分析了脱硝催化剂中毒原因,对催化剂的抗H_(2)O、SO_(2)、碱金属中毒性能进行了探讨,展望了水泥行业SCR中温脱硝催化剂的研究前景。

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。

Study on the mechanism of NH3-selective catalytic reduction over CuCexZr1-x/TiO2

Copper-cerium-zirconium catalysts loaded on Ti02 prepared by a wet impregnation method were investigated for NHz-selective catalytic reduction （SCR） of NOx. The reaction mechanism was proposed on the basis of results from in situ diffuse reflectance infrared transform spectroscopy （DRIFT）. When NH3 is introduced, ammonia bonded to Lewis acid sites is more stable over CuCe0.25Zr0.75/TiO2 at high temperature, while Brensted acid sites are more important than Lewis acid sites at low temperature. For the NH3＋NO＋O2 co-adsorption, NH3 species occupy most of activity sites on CuCe0.25Zr0.75/TiO2 catalyst, and mainly exist in the forms of NH4＋ （at low temperature） and NH3 coordinated （at high temperature）, playing a crucial role in the NHz-SCR process. Two different reaction routes, the L-H mechanism at low temperature （〈 200℃） and the E-R mechanism at high temperature （〉200℃）, are presented for the SCR reaction over C uCe0.25Zr0.75/TiO2 catalyst.

In-situ investigation of melting characteristics of waste selective catalytic reduction catalysts during harmless melting treatment

Selective catalytic reduction(SCR) catalyst waste is a hazardous solid waste that seriously threatens the environment and public health.In this study,a thermal melting technology is proposed for the treatment of waste SCR catalysts.The melting characteristics and mineral phase transformation of waste SCR catalysts blended with three different groups of additives were explored by heating stage microscopy,thermogravimetric analysis/differential scanning calorimetry(TG/DSC) analysis,thermodynamic simulation,and X-ray diffraction(XRD) analysis;heavy metal leaching toxicity was tested by inductively coupled plasma-atomic emission spectrometry(I CP-AES) analysis.The results indicated that the melting point of waste SCR catalysts can be effectively reduced with proper additives.The additive formula of 39.00% Fe2 O3(in weight),6.50% CaO,3.30% SiO2,and 1.20% Al2 O3 achieves the optimal fluxing behavior,significantly decreasing the initial melting temperature from 1223℃ to1169℃.Furthermore,the whole heating process of waste SCR catalysts can be divided into three stages:the solid reaction stage,the sintering stage,and the primary melting stage.The leaching concentrations of V,As,Pb,and Se are significantly reduced,from 10.64,1.054,0.195,and 0.347 mg/L to 0.178,0.025,0.048,and 0.003 mg/L,respectively,much lower than the standard limits after melting treatment,showing the strong immobilization capacity of optimal additives for heavy metals in waste SCR catalysts.The results demonstrate the feasibility of harmless melting treatments for waste SCR catalysts with relatively low energy consumption,providing theoretical support for a novel method of disposing of hazardous waste SCR catalysts.

Multi-stage ammonia production for sorption selective catalytic reduction of NO_(x)

Sorption selective catalytic reduction of nitrogen oxides(NO_(x))(sorption-SCR)has ever been proposed for replacing commercial urea selective catalytic reduction of NO_(x)(urea-SCR),while only the single-stage sorption cycle is hitherto adopted for sorption-SCR.Herein,various multi-stage ammonia production cycles is built to solve the problem of relative high starting temperature with ammonia transfer(AT)unit and help detect the remaining ammonia in ammonia storage and delivery system(ASDS)with ammonia warning(AW)unit.Except for the singlestage ammonia production cycle with MnCl2,other sorption-SCR strategies all present overwhelming advantages over urea-SCR considering the much higher NO_(x) conversion driven by the heat source lower than 100℃ and better matching characteristics with low-temperature catalysts.Furthermore,the required mass of sorbent for each type of sorption-SCR is less than half of the mass of AdBlue for urea-SCR.Therefore,the multifunctional multi-stage sorption-SCR can realize compact and renewable ammonia storage and delivery with low thermal energy consumption and high NO_(x) conversion,which brings a bright potential for efficient commercial de-NO_(x) technology.

废弃SCR催化剂中砷的二次释放行为研究

为了降低废弃SCR催化剂中砷的二次释放对环境的危害,文章应用XRD、XRF、SEM-EDS、ICP-OES等分析手段,采取柱浸出实验方法模拟自然降雨或水蚀条件下废弃SCR催化剂中砷的释放行为及特性,设计了砷的热释放在线监测系统,探索废弃SCR催化剂中砷在受热条件下的二次释放行为。结果表明:(1)废弃SCR催化剂中砷含量高达1.477%;(2)废弃SCR催化剂中砷在酸性水浴条件下(pH=5)析出率可达39.71%,析出率与水浴pH值呈负相关;(3)在受热条件下,废弃SCR催化剂中砷在800~1 000℃温度段可100%释放。因此,废弃SCR催化剂在储存及运输过程中应避免雨水冲刷,采用低温回收方法,可降低废弃或中毒SCR催化剂中砷的二次危害。