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.

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.

Low-Temperature SCR of NO with NH_3 on Mn-Based Catalysts Modified with Cerium

A series of Mn-based catalysts, MnOx, MnOx-CeO, Pd-Mn-Ce, MnOx/AC were prepared. And their performances for NO low-temperature SCR were investigated in this study. The NO conversion is about 90% at 100 ℃ on MnOx-CeOand almost all NO can be converted at 120 ℃. Similar results are also observed in the tests on MnOx-CeO/AC. The excellent low-temperature catalytic activity of modified Mn-based catalysts, which may be mainly due to the oxygen storage function of CeO, can improve the oxygen flow on the catalysts surface. Then the oxidation of NO to NO2 is accelerated, which is the key step of NO SCR.

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.

Redistributing Cu species in Cu-SSZ-13 zeolite as NH3-SCR catalyst via a simple ion-exchange

The nature and distribution of Cu species in Cu-SSZ-13 play a vital role in selective catalytic reduction of NO by NH3(NH3-SCR),but existing methods for adjusting the Cu distribution are complex and difficult to control.Herein,we report a simple and effective ion-exchange approach to regulate the Cu distribution in the one-pot synthesized Cu-SSZ-13 that possesses sufficient initial Cu species and thus provides a“natural environment”for adjusting Cu distribution precisely.By using this proposed strategy,a series of Cu-SSZ-13x zeolites with different Cu contents and distributions were obtained.It is shown that the dealumination of the as-synthesized Cu-SSZ-13 during the ion-exchange generates abundant vacant sites in the double six-membered-rings of the SSZ-13 zeolite for relocating Cu2+species and thus allows the redistribution of the Cu species.The catalytic results showed that the ion-exchanged Cu-SSZ-13 zeolites exhibit quite different catalytic performance in NH3-SCR reaction but superior to the parent counterpart.The structure–activity relationship analysis indicates that the redistribution of Cu species rather than other factors(e.g.,crystallinity,chemical composition,and porous structure)is responsible for the improved NH3-SCR performance and SO_(2) and H_(2)O resistance.Our work offers an effective method to precisely adjust the Cu distribution in preparing the industrial SCR catalysts.

Effect of TiO_2 surface properties on the SCR activity of NOx emission abatement catalyst

NOx emission abatement catalysts V 2O 5 supported on various TiO 2 including anatase, rutile and mixture of both were investigated with various physico\|chemical measurements such as BET, NH\-3\|TPD, NARP, XRD and so on, and the effect of TiO\-2 surface properties on the SCR(selective catalytic reduction) activity of V\-2O\-5/TiO\-2 catalysts was studied. It was found that the TiO\-2 surface properties had strong affect on the SCR activity of V\-2O\-5/TiO\-2 catalysts. The stronger acidic property resulted in the higher exposure of active sites as well as the higher SCR activity.

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.

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.

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.

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.

Comprehensive recovery of W,V,and Ti from spent selective reduction catalysts

In this study,spent WO_(3)/V_(2)O_(5)-TiO_(2) catalysts used for selective catalytic reduction were treated by a hydrometallurgical process to comprehensively recover valuable metallic elements,such as W,V,and Ti.Al and Si impurities were preferentially removed by selective micro wave-assisted alkali leaching.W and V were leached by enhanced high-pressure leaching with efficiencies estimated at 95% and 81%.The leaching of W and V followed the nuclear shrinkage model controlled by the combination of product layer diffusion and interfacial chemical reaction.A synergistic extraction was applied to separate W and V using an extractant mixture of di-(2-ethylhexyl)phosphoric acid P204 and the primary amine N1923.The extraction efficiencies of V and W reached 86.5% and 6.3%,respectively,with a separation coefficient(V/W) of 95.30.The product was precipitated after extraction to yield ammonium paratung state(APT) and NH_(4)VO_(3).The TiO_(2)catalyst carrier residue meets commercial specifications for reuse.This comprehensive recovery process with the characteristics of high-pressure leaching and synergistic extraction realizes the resourceful utilization of the spent catalysts.

NOx Emission Reduction Technology for Marine Engine Based on Tier-Ⅲ:A Review

The development of maritime trade has greatly promoted the development of diesel engines.However,with the increasingly serious environmental problems,more and more attention has been paid to the exhaust emissions of high-power marine diesel engines.The restrictions on SOx have been implemented globally,and the limitation of the NO,will be the next priority.This paper illustrates(a)Principle and research progress of NOx emissions-reduction technology of marine diesel engine;(b)Summary of advantages and disadvantages among various reduction technologies and their reduction effects;(c)The application effect of mainstream technology on board.Firstly,since exhaust gas recirculation(EGR)can achieve Tier-Ⅲ directly from Tier-Ⅰ without considering the increased fuel consumption.It is deemed as the most promising technology to reduce emissions by controlling combustion condition.However,EGR has shortcomings of excessive increase in ftiel consumption and generation of waste water,which need to be solved immediately.Secondly,selective catalytic reduction(SCR)is the most effective and straightforward means to achieve Tier-Ⅲ.Despite of the continuous optimization of SCR unit volume,the problem of scrap catalyst seriously limits its wide application.How to match the supercharger more efficiently is a key factor in choosing between high and low pressure SCR.Thirdly,nature gas(NG)engines are capable of achieving a reduction in NOx,but in order to meet the requirements of Tier-Ⅲ,it still needs to be assisted by other technologies.The emissions of hydrocarbon(HC)and CO in NG engines are huge defects that must be solved.Lastly,technologies such as the Miller cycle,Two-stage supercharging and mixed-water combustion can also reduce emissions but were rarely used alone.These technologies can be combined with EGR,SCR and NG engines to optimize the enginesJ economy and emission characteristics.

Design guidelines for urea hydrolysers for ammonia demand of the SCR DENOX project in coal-fired power plants

Ammonia is highly volatile and will present substantial environmental and operation hazards when leaking into the air. However, ammonia is the most common reactant in the DENOX project to eliminate NOx in the flue gas. The storage and transportation of liquid ammonia has always been a dilemma of the power plant. Urea is a perfect substitute source for ammonia in the plant. Urea hydrolysis technology can easily convert urea into ammonia with low expense. Presently, there is still no self-depended mature urea hydrolysis technology for the DENOX project in China; therefore, this paper proposes several guidelines to design the urea hydrolyser by theoretical analysis. Based on theoretical analysis, a simulation model is built to simulate the chemical reaction in the urea hydrolyser and is validated by the operational data of the commercial hydrolyser revealed in the literature. This paper endeavors to propose suggestions and guidelines to develop domestically urea hydrolysers in China.

Optimizing the crystallinity and acidity of H-SAPO-34 by fluoride for synthesizing Cu/SAPO-34 NH_3-SCR catalyst

A series of H-SAPO-34 zeolites were synthesized by a hydrothermal method in fluoride media.The as-synthesized H-SAPO-34 zeolites were characterized by X-ray diffraction（XRD）,scanning electron microscopy（SEM）,N_2 physisorption,temperature-programmed desorption of NH_3（NH_3-TPD） and nuclear magnetic resonance（NMR） measurements.The results showed that a certain concentration of F- anions promoted the nucleation and crystallization of H-SAPO-34.The H-SAPO-34 synthesized in the fluoride media showed high crystallinity,uniform particle size distribution,large specific surface area and pore volume,and enhanced acidity.Therefore,Cu/SAPO-34 based on the fluoride-assisted zeolite showed a broadened temperature window for the selective catalytic reduction of NO by NH_3（NH_3-SCR） reaction due to the enhanced acidity of the zeolite and the improved dispersion of copper species.

Impact of diesel emission fluid soaking on the performance of Cu-zeolite catalysts for diesel NH3-SCR systems

Diesel emission fluid （DEF） soaking and urea deposits on selective catalytic reduction （SCR） catalysts are critical issues for real diesel engine NH3-SCR systems. To investigate the impact of DEF soaking and urea deposits on SCR catalyst performance, fresh Cu-zeolite catalyst samples were drilled from a full-size SCR catalyst. Those samples were impregnated with DEF solutions and subsequently hydrothermally treated to simulate DEF soaking and urea deposits on real SCR catalysts during diesel engine operations. Their SCR performance was then evaluated in a flow reactor with a four-step test protocol. Test results show that the DEF soaking leached some Cu from the SCR catalysts and slightly reduced their Cu loadings. The loss of Cu and associated metal sites on the catalysts weakened their catalytic oxidation abilities and caused lower NO/NI-I3 oxidation and lower high-temperature N20 selectivity. Lower Cu loading also made the catalysts less active to the decomposition of surface ammonium nitrates and decreased low-temperature N20 selectivity. Cu loss during DEF impregnation released more acid sites on the surface of the catalysts and increased their acidities, and more NH3 was able to be adsorbed and involved in SCR reactions at medium and high temperatures. Due to lower NH3 oxidation and higher NH3 storage, the DEF-impregnated SCR catalyst samples showed higher NOx conversion above 400 ℃ compared with the non-soaked one. The negative impact of urea deposits during DEF impregnation was not clearly observed, because the high-temperature hydrothermal treatment helped to remove the urea deposits.