过渡金属掺杂对MnO_(x)-CeO_(2)低温SCR性能的影响

通过水解驱动氧化还原法合成了掺杂过渡金属的2Mn-Ce-M(M为Fe,Cu,Ni,Cr)催化剂,考察了过渡金属掺杂对低温SCR脱硝性能的影响.其中2Mn-Ce-0.2Cr催化剂比表面积较大,氧化还原能力适中,具有丰富的酸性位点和氧空位、最高的化学吸附氧含量及酸位强度,有利于低温下NH_(3)-SCR反应的顺利进行.2Mn-Ce-0.2Cr催化剂的低温NH_(3)-SCR活性最好,能在100~225℃的宽温度区间内保持80%以上的NO_(x)转化率,在125℃时NO_(x)转化率更是达到99.1%,为中低温催化还原烟气中的NO_(x)提供了新思路.此外,2Mn-Ce-0.2Cr还具有良好的抗硫抗水能力,在150℃下,加入40×10^(-6)的SO_(2)反应5 h,其催化活性稳定在98%;在3%的水蒸气下,其效率保持在95%以上.

MnO_(x)-CeO_(2)催化剂的氯苯氧化性能及反应机理

研究了Mn/Ce摩尔比、反应温度、氧气和水对MnO_(x)-CeO_(2)催化剂催化氯苯氧化性能(活性、选择性和稳定性)的影响,并分析了其理化性能、作用过程和反应机理.结果表明,在含H_(2)Ogas和O_(2)(体积分数均为5%)条件下,Mn_(2)Ce_(1)O_(x)在100,200和300℃下分别取得了80.6%,86.8%和97.5%的氯苯转化率;反应温度和氧气含量的增加及水的存在均有利于提高催化活性和反应稳定性;MnO_(x)和CeO_(2)复合提高了比表面积(128.61 m^(2)/g)、降低了孔径(6.17 nm)且增强了表面酸性(中酸和强酸位点)和氧化还原能力,价态电子交互循环过程(Ce^(4+)/Ce^(3+)←→—Mn^(4+)/Mn^(3+)/Mn_(2)+)和氧循环作用(吸附氧←→—晶格氧)是催化反应的关键驱动过程.氯苯分子吸附在Mn_(2)Ce_(1)O_(x)催化剂表面发生脱氯反应形成苯酚,进一步开环氧化为关键的乙酸盐中间物种,最终转化为CO_(2),HCl或Cl_(2),H_(2)O.水和氧气可以活化为羟基和[O*]等活性氧物种,促进了氯苯的吸附活化和中间产物的深度氧化,降低了中间副产物(氯代乙氧基、苯酚和醛类等)的形成与表面Cl物种的沉积,进而提升了催化活性和反应稳定性.

MnO_(x)-CeO_(2)和Co_(3)O_(4)-CeO_(2)催化氧化甲醛的性能研究

采用水热合成法制备Ce-MOF载体,通过浸渍氧化锰、氧化钴的前驱体后得到催化剂MnO_(x)-CeO_(2)和Co_(3)O_(4)-CeO_(2)。研究表明,催化剂Co_(3)O_(4)-CeO_(2)在120℃时甲醛转化率为79.11%。MnO_(x)-CeO_(2)的催化性能最优,当温度为100℃时,可以将甲醛完全转化为H_(2)O和CO_(2)。通过X-射线衍射(XRD)、程序升温还原(H_(2)-TPR)和程序升温脱附(O_(2)-TPD)进行表征,说明加入Mn既有利于CeO_(2)表面氧物种的迁移,促进氧物种的脱附,又有利于表面氧在CeO_(2)的还原性,促进还原过程中的氧转移。结果表明,MnO_(x)-CeO_(2)低温时较强的还原能力以及其丰富的表面氧物种有利于提高催化剂的催化性能。

MnO_(x)-CeO_(2)催化剂在低温下催化氧化低浓度甲醛的性能研究

采用修饰共沉淀法制得铈锰氧化物MnO_(x)-CeO_(2)催化剂,采用环境舱法,模拟太阳光在贴近真实夏季车内环境的低温低浓度工况下,考察太阳辐射强度、甲醛初始浓度对MnO_(x)-CeO_(2)热催化甲醛的性能影响,并进行催化动力学探究。结果表明,该催化剂孔道结构丰富,光热转化能力优秀,与单独的铈锰氧化物相比氧化能力有明显提升。在太阳辐射强度为450~650 W/m^(2)时,初始浓度为0.5 mg/m^(3)的甲醛降解率可达76.2%~82.1%,且E-R模型更贴近该实验数据。在太阳辐射强度为550 W/m^(2),初始浓度分别为0.2,0.5,1.0 mg/m^(3)时,降解率分别为63%,70.6%,78.3%,降解效果明显。此外,5种催化剂(MnO_(x)-CeO_(2)、MnO_(x)-CeO_(2)-TiO_(2)、TiO_(2)、Bi-V-O、CuO-MnO_(2))在相同实验条件下的甲醛催化效果表明,MnO_(x)-CeO_(2)降解率最高,为78.3%。该催化剂具备良好的稳定性。表明该催化剂在车内等低温低浓度环境下的甲醛催化氧化有着广泛的应用前景。

Enhancement in the Hg^(0) oxidation efficiency and sulfur resistance of CuCl_(2)-modified MnO_(x)-CeO_(x) nanorod catalysts

In this study,a series of CuCl_(2)-modified MnO_(x)-CeO_(x)nanorods were synthesized for the oxidation of Hg^(0).The addition of CuCl_(2)resulted in an enhancement in the catalyst’s Hg^(0)oxidation ability,and Hg^(0)oxidation efficiency reached>97%from 150 to 250°C.In the MnO_(x)-CeO_(x)catalysts,Mn^(4+)played the role of the active species for Hg^(0)oxidization,but in the CuCl_(2)-doped catalysts Cl−also contributed to Hg^(0)oxidation,conferring the superior performance of these samples.The introduction of SO_(2) led to a decrease in the availability of Mn^(4+),and the Hg^(0)oxidation efficiency of MnO_(x)-CeO_(x)decreased from about 100%to about 78%.By contrast,CuCl_(2)-promoted samples maintained a Hg^(0)oxidation efficiency of about 100%during the SO_(2) deactivation cycle due to the high reactivity of Cl−.

Mechanistic investigation on the Hg^(0)elimination ability of MnO_(x)-CeO_(x)nanorod adsorbents:effects of Mn/Ce molar ratio

Mercury pollution is created by coal combustion processes in multi-component systems.Adsorbent injection was identified as a potential strategy for capturing Hg^(0)from waste gases,with adsorbents serving as the primary component.The hydro-thermal approach was used to synthesize a series of MnO_(x)-CeO_(x)nanorod adsorbents with varying Mn/Ce molar ratios to maximize the Hg^(0)capture capabilities.Virgin CeO,had weak Hg elimination activity;<8%Hg^(0)removal efficiency was obtained from 150℃to 250℃.With the addition of MnOr,the amount of surface acid sites and the relative concentration of Mn4+increased.This ensured the sufficient adsorption and oxidation of Hg while overcoming the limitations of restricted adsorbate-adsorbent interactions caused by the lower surface area,endowing MnO_(x)-CeO_(x)with increased Hg^(0)removal capac-ity.When the molar ratio of Mn/Ce reached 6/4,the adsorbent's Hg^(0)removal efficiency remained over 92%at 150℃and 200℃.As the molar ratio of Mn/Ce grew,the adsorbent's Hg^(0)elimination capacity declined due to decreased surface area,weakened acidity,and decreased activity of Mn^(4+);<75%Hg^(0)removal efficiency was reached between 150℃and 250℃for virgin MnOx.Throughout the overall Hg'elimination reactions,Mn4+and O.were in charge of oxidizing Hg^(0)to Hg^(0),with Ce^(4+)acting as a promoter to aid in the regeneration of Mn^(4+),Because of its limited adaptability to flue gas components,further optimization of the MnO_(x)-CeO_(x)nanorod adsorbent is required.

Extruded monolith MnO_(x)-CeO_(2)-TiO_(2) catalyst for NH_(3)-SCR of low temperature flue gas from an industry boiler:Deactivation and recovery

The selective catalytic reduction(SCR) of NO_(x) with NH_(3)(NH_(3)-SCR) technology has been widely applied for reducing NO_(x) emissions from stationary and mobile sources.In this work,the extruded monolith MnO_(x)-CeO_(2)-TiO_(2) catalyst was installed in a cement kiln for NH_(3)-SCR of NO_(x),where the flue gas temperature was 110-140℃.It is found that the monolith catalyst is severely deactivated after operating for about 200 h with almost no NO_(x) conversion at 160℃ under GHSV of 50000 h^(-1),while the fresh monolith catalyst remains 60% NO_(x) conversion.Scanning electron microscopy-energy dispersive spectroscopy(SEM-EDS),X-ray photoelectron spectroscopy(XPS),temperature-programmed desorption of SO_(2)(SO_(2)-TPD) and thermogravimetric-differential thermal analysis(TG-DTG) experiments reveal that both MnO_(x) and CeO_(2) oxides in monolith are severely sulfated to manganese sulfate and cerium sulfate,and the external monolith walls are covered by massive ceria sulfate and little ammonium nitrate.In situ diffuse reflectance infrared Fourier trans form spectroscopy(DRIFTS) analysis demonstrates that the formation of nitrates at low temperatures is inhibited due to the occupation of active sites in MnO_(x)-CeO_(2)-TiO_(2) by sulfates,resulting in the decrease of low temperature activity.After washing with water,the activity of deactivated monolith catalyst can be partially recovered,together with significant loss of manganese and cerium from monolith.

Low-temperature selective catalytic reduction of NO with NH_(3) based on MnO_(x)-CeO_(x)/ACFN

MnO_(x)-CeO_(x)/ACFN were prepared by the impregnation method and used as catalyst for selective catalytic reduction of NO with NH_(3) at 80℃-150℃.The catalyst was characterized by N_(2)-BET,scanning electron microscopy(SEM)and Fourier transform infrared spectroscopy(FT-IR).The fraction of the mesopore and the oxygen functional groups on the surface of activated carbon fiber(ACF)increased after the treatment with nitric acid,which was favorable to improve the catalytic activities of MnO_(x)-CeO_(x)/ACFN.The experimental results show that the conversion of NO is nearly 100%in the range 100℃-150℃under the optimal preparation conditions of MnO_(x)-CeO_(x)/ACFN.In addition,the effects of a series of performance parameters,including initial NH3 concentration,NO concentration and O_(2) concentration,on the conversion of NO were studied.

Activity enhancement of acetate precursor prepared on MnO_(x)-CeO_(2) catalyst for low-temperature NH_(3)-SCR: Effect of gaseous acetone addition

MnO_(x)-CeO_(2) catalysts are developed by hydrolysis driving redox method using acetate precursor(3 Mn1 Ce-Ac) and nitrate precursor(3 Mn1 Ce-N) for the selective catalytic reduction(SCR) of NO_(x) by NH_(3).A counterpart sample(Cop-3 Mn1 Ce) was prepared by the NH_(3)·H_(2) O co-precipitation method for comparison purpose.Combining the results of physicochemical properties characterization and performance test,we find that the 3 Mn1 Ce-Ac catalyst with some nanorod structures is highly active for the deNOx process.The SCR activity of the 3 Mn1 Ce-Ac catalyst is more admirable than the 3 Mn1 Ce-N and the Cop-3 Mn1 Ce catalysts due to plentiful Lewis acid sites,excellent low-temperature reducibility,and superior surface area resulted from O_(2) generation during the pre paration procedure.The 3 Mn1 Ce-Ac still exhibits the greatest performance for the deNO_(x )process when gaseous acetone is in the SCR feed gas.The NOx conversion and N2 selectivity over the 3 Mn1 Ce-Ac are both improved by gaseous acetone above150℃ due to the inhibition of SCR undesired side reactions(NSCR & C-O reactions) and "slow-SCR" process.

Enhanced catalytic activity for simultaneous removal of PCDD/Fs and NO over carbon nanotubes modified MnO_(x)-CeO_(2)/TiO_(2)catalyst at low temperatu

Simultaneous catalytic removal of polychlorinated dibenzo-p-dioxins and dibenzofurans(PCDD/Fs)and nitrogen oxides(NO_(x))emission at low temperature is of great significance to solve the multiple air pollution problem caused during waste incineration.A novel catalyst with excellent low-temperature activity towards PCDD/Fs catalytic decomposition,as well as selective catalytic reduction(SCR)of NO with NH_(3)is urgently needed to simultaneously control PCDD/Fs and NO emis-sions.Manganese-cerium composite oxides supported on titanium dioxide(MnO_(x)-CeO_(2)/TiO_(2))or TiO_(2)and carbon nano-tubes(CNTs)composite carrier(MnO_(x)-CeO_(2)/TiO_(2)-CNTs)were prepared using sol-gel method,and their catalytic activity towards simultaneous abatement of ortho-dichlorobenzene(o-DCBz,model molecular to simulate PCDD/Fs)and NO was investigated.In comparison with their removal,the simultaneous removal efficiencies of o-DCBz and NO over MnO_(x)-CeO_(2)/TiO_(2)catalyst are lowered to 27.9%and 51.3%at 150℃under the gas hourly space velocity(GHSV)of 15,000 h−1,due to the competition between the reactants for the limited surface acid sites and surface reactive oxygen species.CNTs addition improves the catalytic activity for their simultaneous removal.The optimum condition occurs on MnO_(x)-CeO_(2)/TiO_(2)combined with 20 wt.%CNTs that above 70%of o-DCBz and NO are removed simultaneously.Characterization results reveal that MnO_(x)-CeO_(2)/TiO_(2)-CNTs catalyst with proper CNTs content has larger Brunauer-Emmet-Teller surface area and greatly improved surface acidity property,which are beneficial to both o-DCBz and NO adsorption.Moreover,the relatively higher surface atomic concentration of Mn^(4+)as well as the existence of abundant surface Ce^(3+)atom accelerates the redox cycle of the catalyst and enriches the surface reactive oxygen species.All the above factors alleviate the competition effect between o-DCBz catalytic oxidation and NH_(3)-SCR reaction and are conducive to the simultaneous abatement of o-DCBz and NO.However,excess CNTs make less contribution on enhancing the interaction between Mn atom and Ce atom,thereby result-ing in less improvement in the catalytic activity.