Vanadium-based compounds and heterostructures as functional sulfur catalysts for lithium-sulfur battery cathodes

Lithium-sulfur(Li-S)batteries have attracted wide attention for their high theoretical energy density,low cost,and environmental friendliness.However,the shuttle effect of polysulfides and the insulation of active materials severely restrict the development of Li-S batteries.Constructing conductive sulfur scaffolds with catalytic conversion capability for cathodes is an efficient approach to solving above issues.Vanadium-based compounds and their heterostructures have recently emerged as functional sulfur catalysts supported on conductive scaffolds.These compounds interact with polysulfides via different mechanisms to alleviate the shuttle effect and accelerate the redox kinetics,leading to higher Coulombic efficiency and enhanced sulfur utilization.Reports on vanadium-based nanomaterials in Li-S batteries have been steadily increasing over the past several years.In this review,first,we provide an overview of the synthesis of vanadium-based compounds and heterostructures.Then,we discuss the interactions and constitutive relationships between vanadium-based catalysts and polysulfides formed at sulfur cathodes.We summarize the mechanisms that contribute to the enhancement of electrochemical performance for various types of vanadium-based catalysts,thus providing insights for the rational design of sulfur catalysts.Finally,we offer a perspective on the future directions for the research and development of vanadium-based sulfur catalysts.

Influence of preparation methods on the physicochemical properties and catalytic performance of MnO_x-CeO_2 catalysts for NH_3-SCR at low temperature

This work examines the influence of preparation methods on the physicochemical properties and catalytic performance of MnOx‐CeO2 catalysts for selective catalytic reduction of NO by NH3 (NH3‐SCR) at low temperature. Five different methods, namely, mechanical mixing, impregnation,hydrothermal treatment, co‐precipitation, and a sol‐gel technique, were used to synthesizeMnOx‐CeO2 catalysts. The catalysts were characterized in detail, and an NH3‐SCR model reaction waschosen to evaluate the catalytic performance. The results showed that the preparation methodsaffected the catalytic performance in the order: hydrothermal treatment > sol‐gel > co‐precipitation> impregnation > mechanical mixing. This order correlated with the surface Ce3+ and Mn4+ content,oxygen vacancies and surface adsorbed oxygen species concentration, and the amount of acidic sitesand acidic strength. This trend is related to redox interactions between MnOx and CeO2. The catalystformed by a hydrothermal treatment exhibited excellent physicochemical properties, optimal catalyticperformance, and good H2O resistance in NH3‐SCR reaction. This was attributed to incorporationof Mnn+ into the CeO2 lattice to form a uniform ceria‐based solid solution (containing Mn‐O‐Cestructures). Strengthening of the electronic interactions between MnOx and CeO2, driven by thehigh‐temperature and high‐pressure conditions during the hydrothermal treatment also improved the catalyst characteristics. Thus, the hydrothermal treatment method is an efficient and environment‐friendly route to synthesizing low‐temperature denitrification (deNOx) catalysts.

Effects of Atmospheres and Precursors on MnO_x/TiO_2 Catalysts for NH_3-SCR at Low Temperature

The effects of atmospheres and precursors on MnOx/TiO2 catalysts were studied, which were prepared by the impregnation method and tested for their NOx conversion activity in ammonia selective catalytic reduction （NH3-SCR） reactions. Results showed that the manganese carbonate （MC） precursor caused mainly Mn2O3, while the manganese nitrate （MN） precursor resulted primarily in MnO2 and the manganese sulfate （MS） precursor was unchanged. The manganese acetate （MA） precursor leaded obtaining a mixture of Mn2O3 and Mn304. NOn conversion decreased in the following order： MA/TiO2 〉 MC/TiO2 〉 MN/TiO2 〉 MS/TiO2 〉 P25, with a calcination temperature of 773 K in air. Catalysts that were prepared by MA and calcined in oxygen performed strong interaction between Ti and Mn, while MnTiO3 was observed. Compared to the catalysts calcined in nitrogen, those calcined in oxygen had larger diameter and smaller surface area and pore. Catalysts that were prepared by MA and calcined in nitrogen tended to gain higher denitration rates than those in air, since they could be prepared with significant specific surface areas. NO., conversion decreased with calcination atmospheres： Nitrogen〉 Air〉 Oxygen. Meanwhile, amorphous Mn2O3 turned into crystalline Mn2O3, when the temperatures increased from 673 to 873 K.

废SCR脱硝催化剂碱式焙烧—水浸提取钒和钨

利用碱式焙烧—水浸工艺提取废SCR脱硝催化剂中的钒和钨,以便后续钒和钨的资源化利用。探究了焙烧温度、焙烧时间、Na_(2)CO_(3)与废催化剂的质量比、水浸温度、水浸时间等对钒和钨浸出效果的影响,结合焙烧产物XRD分析探究其焙烧机理。结果表明,废SCR脱硝催化剂合适的碱式焙烧—水浸条件为:焙烧温度875℃、焙烧时间1.5 h、Na_(2)CO_(3)与废催化剂的质量比1∶1、水浸温度80℃、水浸时间2 h,在此条件下钒和钨的浸出率分别达到91.33%和96.34%。根据XRD分析结果,在碱式焙烧过程中钒和钨分别转化为易溶性的NaV6O15和Na2WO4;经过碱式焙烧—水浸处理后,90%以上的钒和钨进入水浸液,而进入水浸液中的钛不足2%。

高NO_(x)浓度低空速下SCR系统的工艺优化

在丙烯腈催化剂的生产过程中,由于硝酸盐的高温分解,有大量高浓度的NO_(x)烟气产生。选择性催化还原法(SCR)是使还原剂氨(NH_(3))与氮氧化物反应后生成氮气(N_(2))与水(H_(2)O)。为使NO_(x)达标排放,生产单位采用选择性催化还原法(SCR)NO_(x)环保处理工艺。该工艺使用尿素[(NH_(2))_(2)CO]水溶液热解取得还原剂NH_(3),相较于直接使用NH_(3)更为安全、环保。通过对丙烯腈催化剂生产装置SCR系统进行工艺条件试验,取得了在低空速工况下去除高浓度NO_(x)的优化工艺条件。试验结果表明,反应温度控制在325~335℃,入口NO_(x)浓度控制在3000μL/L以下,氨氮比保持在1.1~1.4,空速保持在620~700h^(-1)(对应尿素热解风的风量在320~370m^(3)/h),SCR系统的NO_(x)去除率保持在95%及以上且NO_(2)的去除率也保持在90%左右的高水平上。试验结果得到了实际运行的验证。在本文观察范围内,NO的去除率在各种工况下均能保持97%以上的高水平,影响NO_(x)去除率的主要因素是NO_(2)的去除率。

Study on Co-Effect of K₂SO₄Deposition and Low Concentration SO₂on Performances of V₂O₅/AC Catalysts for Low Temperature SCR

Simulated compounds were prepared by loading K2SO4 onto V2O5/AC catalysts. Study the effect of K2SO4 on V1/AC catalysts in the presence of low concentration SO2. Transient response techniques, TPD was carried out. The results indicated that the DeNO activity of V1/AC catalysts was decreased seriously in the early period of operation, but the deactivation was gradually diminished with SO2 adsorption and then, it was completely eliminated. For the sulphated catalysts (saturated catalysts by sulphate), their SCR activity were free from existence of gaseous SO2. the loss of activity about 10% caused by K2SO4 was found on them. The deactivation of K2SO4 deposited catalysts was due to the decrease of adsorbed and activated NH3, or some acid sites.

SCR烟气脱硝催化剂再生车间废水处理技术研究进展

工业污染源排放的氮氧化物主要来源于燃煤过程,选择性催化还原法(SCR)脱硝技术因脱硝效果稳定、脱硝效率高、选择性强等特点被广泛应用于氮氧化物的减排,但该方法每年会产生大量的废弃脱硝催化剂,催化剂受烟气的污染富含砷、铬等重金属,已被国家纳入危险废物进行管理,废弃催化剂的再生利用成为当前行业发展的必然需求。就当前SCR烟气脱硝催化剂再生过程中产生的废水特征进行分类,针对废水中不同特征的污染因子,分别就其处理技术研究进展进行分析,并提出合理的再生废水处理工艺建议。

NH_(3)SO_(3)改性稀土尾矿催化剂NH_(3)-SCR脱硝活性及SO_(2)/H_(2)O耐受性能研究

采用球磨、微波焙烧方法制备了不同质量分数NH_(3)SO_(3)改性稀土尾矿NH_(3)-SCR脱硝催化剂。通过BET、SEM-EDS、XRD、NH_(3)-TPD、H_(2)-TPR分析了催化剂脱硝活性及SO_(2)/H_(2)O耐受性能。结果表明:NH_(3)SO_(3)改性使催化剂脱硝活性得到了显著提高,10%NH_(3)SO_(3)改性催化剂在300~350℃脱硝活性可达90%左右。SO_(2)/H_(2)O共同作用可将10%NH_(3)SO_(3)改性催化剂脱硝活性提高至97%,其促进作用保持了良好的稳定性,且具有可逆性。NH_(3)SO_(3)改性稀土尾矿后,催化剂比表面积、酸性位点及强度增加,表面活性物质分散度更高,弱化了尾矿矿物晶型,提高了催化剂吸附能力和氧化还原能力,从而提高催化脱硝活性,同时具备优良的SO_(2)/H_(2)O耐受性。

The effect of cations(NH_4^+,Na^+,K^+,and Ca^(2+)) on chemical deactivation of commercial SCR catalyst by bromides

Alkali and alkaline‐earth metals from fly ash have a significant deactivation effect on catalysts used for selective catalytic reduction of NOx by NH3(NH3‐SCR).Bromides are considered effective additives to improve Hg0 oxidation on SCR catalysts.In this work,the effects of different bromides(NH4Br,NaBr,KBr,and CaBr2)on a commercial V2O5‐WO3/TiO2 catalyst were studied.NOx conversion decreased significantly over the KBr‐poisoned catalyst(denoted as L‐KBr),while that over NaBr‐and CaBr2‐poisoned catalysts(denoted as L‐NaBr and L‐CaBr,respectivity)decreased to a lesser extent compared with the fresh sample.Poor N2 selectivity was observed over L‐NaBr,L‐KBr and L‐CaBr catalysts.The decrease in the ratio of chemisorbed oxygen to total surface oxygen(Oα/(Oα+Oβ+Ow)),reducibility and surface acidity might contribute to the poor activity and N2 selectivity over L‐KBr catalyst.The increased Oαratio was conducive to the enhanced reducibility of L‐CaBr.Combined with enhanced surface acidity,this might offset the negative effect of the loss of active sites by CaBr2 covering.The overoxidation of NH3 and poor N2 selectivity in NH3 oxidation should retard the SCR activity at high temperatures over L‐CaBr catalyst.The increased basicity might contribute to increased NOx adsorption on L‐KBr and L‐CaBr catalysts.A correlation between the acid‐basic and redox properties of bromide‐poisoned catalysts and their catalytic properties is established.

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.

Sustainable recycling of titanium from TiO_(2) in spent SCR denitration catalyst via molten salt electrolysis

Spent catalyst used for denitration by selective catalytic reduction(spent SCR denitration catalysts) is one of the important urban mines due to the high content of TiO_(2)(~85 wt%) and the massive accumulation amount(over 100,000 tons),therefore,value-added reutilization of titanium in spent SCR catalysts is considerably meaningful.In this paper,a novel method is proposed for converting the titanium oxide in spent SCR denitration catalysts to metallic titanium.Specifically,titanium dioxide(TiO_(2)) was firstly obtained from spent SCR denitration catalysts after removing the impurities by hydrometallurgy process.Then,TiO_(2) is converted to Ti_(2)CO by carbothermic reduction method,and Ti_(2)CO was further purified by oleic acid capture.Finally,by utilizing the as-prepared Ti_(2)CO as the consumable anode in the NaCl-KCl molten salt,high-purity metallic titanium was deposited at cathode,all confirming the feasibility for the conversion of low-grade TiO_(2) in the spent catalysts,from 60 wt% to high-purity metallic Ti(99.5 wt%), furthermore,the energy consumption of this process is 3950 kWh tonne-1 Ti,which is lower than that of most traditional titanium metallurgy methods.The method herein can provide new insights for the value-added recycling of titanium resources in urban mines.

Mn/TiO_(2)低温SCR催化剂钾中毒机理研究

Mn/TiO_(2)具有良好的低温NH3选择性催化还原NOx(SCR)的活性。烟气中存在的碱金属会从物理和化学上毒害催化剂导致Mn/TiO_(2)催化剂中毒失活。论文以暴露{101}面TiO_(2)为载体制备Mn/TiO_(2)催化剂,采用浸渍法制备K中毒催化剂,研究了Mn/TiO_(2)低温SCR催化剂钾中毒机理。实验发现,Mn/TiO_(2)催化剂脱硝效率随K中毒浓度增加而减少;新鲜Mn/TiO_(2)催化剂表面NH3-SCR反应由E-R和L-H机理共同控制;K吸附会导致催化剂比表面积降低,催化剂表面Mn4+、化学吸附氧比例降低,表面酸性位点数量减少,导致脱硝活性降低;同时K更易吸附在Mn顶位以及桥接O位附近,导致NO的吸附活化受到严重遏制,同时削弱NH3的吸附,使得L-H机理受到阻断,只能以E-R机理控制为主。

TiO2 preparation by improved homogeneous precipitation and application in SCR catalyst

Ultrasonic treatment and hydrothermal method were applied in the traditional homogeneous precipitation for nano-TiO_2 preparation, which was used as carrier material for the production of honeycomb selective catalytic reduction(SCR) catalyst. The influence rules of the two improved methods on characterization of TiO_2 samples, denitration activity and mechanical strength of honeycomb SCR catalyst samples were mainly focused on. The results indicate that the specific surface area, particle size and uniformity of TiO_2 samples are significantly improved by both of the ultrasonic and hydrothermal treatments compared with the traditional homogeneous precipitation. Also, the denitration activities of catalyst samples are enhanced by the two improved methods(the NO_x reduction ratio increases from 88.89% to 95.45% by ultrasonic homogeneous precipitation process, and to 94.12% by hydrothermal homogeneous precipitation process). On the other hand, because of good spherical shape and high particle distribution of TiO_2 sample from hydrothermal homogeneous precipitation process, the corresponding honeycomb catalyst samples get the best mechanical strength, which is even higher than that of the reference sample from commercial nano-TiO_2. So, it is concluded that the hydrothermal homogeneous precipitation can be a feasible and effective preparation method of TiO_2 carrier for the honeycomb SCR catalyst production.

Doping effect of cations(Zr^(4+),Al^(3+),and Si^(4+)) on MnO_x/CeO_2 nano-rod catalyst for NH_3-SCR reaction at low temperature

Thermally stable Zr4+, Al3+, and Si4+ cations were incorporated into the lattice of CeO2 nano‐rods (i.e., CeO2‐NR) in order to improve the specific surface area. The undoped and Zr4+, Al3+, and Si4+ doped nano‐rods were used as supports to prepare MnOx/CeO2‐NR, MnOx/CZ‐NR, MnOx/CA‐NR, and MnOx/CS‐NR catalysts, respectively. The prepared supports and catalysts were comprehensively characterized by transmission electron microscopy (TEM), high‐resolution TEM, X‐ray diffraction, Raman and N2‐physisorption analyses, hydrogen temperature‐programmed reduction, ammonia temperature‐programmed desorption, in situ diffuse reflectance infrared Fourier‐transform spectroscopic analysis of the NH3 adsorption, and X‐ray photoelectron spectroscopy. Moreover, the catalytic performance and H2O+SO2 tolerance of these samples were evaluated through NH3‐selective catalytic reduction (NH3‐SCR) in the absence or presence of H2O and SO2. The obtained results show that the MnOx/CS‐NR catalyst exhibits the highest NOx conversion and the lowest N2O concentration, which result from the largest number of oxygen vacancies and acid sites, the highest Mn4+ content, and the lowest redox ability. The MnOx/CS‐NR catalyst also presents excellent resistance to H2O and SO2. All of these phenomena suggest that Si4+ is the optimal dopant for the MnOx/CeO2‐NR catalyst.

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.

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.

Recovery of vanadium and tungsten from waste selective catalytic reduction catalysts by K_(2)CO_(3) roasting and water leaching followed by CaCl_(2) precipitation

Waste selective catalytic reduction(SCR)catalysts are potential environmental hazards.In this study,the recovery of vanadium and tungsten from waste SCR catalysts by K_(2)CO_(3)roasting and water leaching was investigated.The roasting and leaching conditions were optimized:the leaching efficiencies of vanadium and tungsten were 91.19%and 85.36%,respectively,when 18 equivalents of K_(2)CO_(3)were added to perform the roasting at 900℃ for 2 h,followed by leaching at 90°C for 1 h.Notably,in the described conditions,the leaching rate of silicon was only 28.55%.Titanates,including K_(2)Ti_(6)O_(13)and KTi8017,were also produced.Si removal was achieved in 85%efficiency adjusting the pH to 9.5,and the Si impurity thus isolated was composed of amorphous Si.Tungsten and vanadium were precipitated using CaCl_(2).At pH 10 and following the addition of 0.10 mol of H_(2)O_(2)and 16 equivalents of CaCl_(2),the precipitating efficiencies of tungsten and vanadium were 96.89%and 99.65%,respectively.The overall yield of tungsten and vanadium was 82.71%and 90.87%,respectively.

废SCR脱硝催化剂碱性浸出液制备白钨精矿工艺研究

目前,通常采用氢氧化钠碱浸法从废SCR脱硝催化剂中提取钨,得到含钨碱性浸出液。该浸出液中除钨之外还含有钒、硅、硫等杂质元素,并且由于溶液碱浓度较高,传统的萃取和吸附方法难以实施,传统盐酸中和-氯化钙沉淀法则会引入Cl-导致设备腐蚀。本文提出了一种新的硫酸镁脱硅-氧化钙沉淀工艺,进行除硅沉钨,制备白钨精矿。在硫酸镁脱硅过程中,通过使用硫酸来调节体系pH值为11,在镁硅摩尔比为0.9的条件下,可达到97.6%的硅脱除率。利用氧化钙将脱硅液沉淀生产白钨精矿,在钙钨摩尔比为1.1、温度108℃沸腾的最佳工艺条件下,得到的白钨精矿产品中WO3含量达到74.69%,硫含量为0.90%,硅含量为1.00%,满足YS/T 231—2015白钨精矿一级品标准。该工艺实现了废SCR脱硝催化剂碱性浸出液中钨的高效回收,同时避免了传统盐酸中和-氯化钙沉淀制备白钨精矿过程中引入Cl-可能导致设备腐蚀的问题。

废SCR催化剂含钒砷碱浸液选择性分离工艺

碱浸法被广泛应用于从废脱硝催化剂中浸取回收钒、钨等有价资源。由于钒和砷的化学性质相似,在碱浸过程中,砷与钒一同溶解到浸出液,导致后续钒元素回收困难,并且处理过程产生有毒废水,危害环境安全。提出了同步钙沉—酸溶—铁盐除砷—钙盐沉钒工艺,在钙沉过程中,通过加入氢氧化钙将钒和砷转化为钒酸钙和砷酸钙固定下来,实现了钒砷高效沉淀与碱溶液回收。酸溶后,采用硫酸亚铁沉淀法实现了酸液中钒砷的有效分离,砷以砷酸铁的形式固定在沉淀渣中。最佳工艺条件为:H 2O 2预氧化30 min、溶液初始pH=3.0、反应温度30℃、反应时间3 h。砷的沉淀率为97.26%,钒的损失率为1.84%。向获得的含钒滤液中加入氢氧化钙得到钒酸钙。该工艺实现了废SCR脱硝催化剂碱性浸出液中钒、砷的高效分离,同时实现了高碱度溶液的回收。

3D Simulation Research on Urea-SCR DeNO_x Catalyst for Diesel Engine

In order to reduce oxides of nitrogen （NOx） emanated from a diesel engine, a comprehensive urea selective catalyst reduction （SCR） DeNOx catalyst was modeled in which numerical simulations were used as a complementary tool for the experimental investigations to make the design decisions, and hence shorten the de- velopment process. In this approach, relevant conversion reactions were studied in 1D model, and the parame- ters obtained in this way were transferred to 3D simulations. According to the results of the study, the conver- sion of NO and NO2 increased with the increase in monolith solid temperature. With the increase in the ratio of NO2/NOx the conversion of NO, NO2 and NOx increased resulting in maximum reduction of NOxat the ratio of 1; beyond this ratio, the conversion of NO2 and NOx decreased; however, NO continued to be converted till the ratio was 1.8. The conversion of NOx decreased with the increase in space velocity.