One-pot synthesis of Fe/Cu-SSZ-13 catalyst and its highly efficient performance for the selective catalytic reduction of nitrogen oxide with ammonia

Series of Fe/Cu-SSZ-13 catalysts with different Fe loading content were synthesized by simple one-pot strategy. The obtained catalysts were subjected to selective catalytic reduction (SCR) of NO_x with NH₃ and were characterized by various techniques. The results show that Fe_0.63/Cu_1.50-SSZ-13 catalyst with proper Fe content exhibits excellent catalytic activity with widest operation temperature window from 160 to 580°C, excellent hydrothermal stability as well as good resistance to sulfur poisoning when compared with Cu-SSZ-13, signifying its great potential for practical applications. Further characterizations reveal that the synthesized Fe/Cu-SSZ-13 catalysts present typical chabazite (CHA) structure with good crystallinity, while isolated Cu²⁺ and monomeric Fe³⁺ are revealed as the predominant copper and iron species. At low temperatures, isolated Cu²⁺ species act as primary active sites for SCR reaction, while monomeric Fe³⁺ species provide sufficient active sites for sustain the SCR activity at high temperature. Moreover, Fe over doping would lead to the damage of zeolite structure, destruction of isolated Cu²⁺ site, as well as the formation of highly oxidizing Fe₂O₃, thus causing deterioration of catalytic performances.     

铜前驱体对Cu/SSZ-13催化剂选择性催化氧化NH3性能的影响

采用浸渍法制备了一系列Cu/SSZ-13(X)催化剂,考察不同铜前驱体对催化剂选择性催化氧化氨(NH_3-SCO)性能的影响,并通过ICP、N_2吸附-脱附、XRD、XPS、EPR、UV-Vis、NH_3-TPD和H_2-TPR等手段对催化剂进行物化性质表征.活性测试结果表明,不同铜前驱体制备的Cu/SSZ-13催化剂活性顺序为Cu/SSZ-13(N) Cu/SSZ-13(AC) Cu/SSZ-13(Cl) Cu/SSZ-13(O).其中Cu/SSZ-13(N)具有最佳的低温活性,在200℃反应温度下NH_3转化率达85.5%,且N_2选择性达到80%以上.XRD、EPR和UV-Vis分析表明,CuO和孤立Cu~(2+)是Cu/SSZ-13催化剂的主要铜物种.NH_3-TPD分析表明,以硝酸铜为前驱体制备的Cu/SSZ-13(N)具有更多的酸性位点,有利于提高催化剂的NH_3吸附能力.H_2-TPR结果表明,Cu/SSZ-13(N)的氧化还原性最强,具有最优异的NH_3活化能力,从而使催化剂呈现最好的低温NH_3-SCO活性.     

Effect of manufacturing methods of AgCl/Al2O3 catalyst on selective catalytic reduction of NOx

The AgCl/Al2O3 catalyst has potential for use in the selective catalytic reduction (SCR) of NOx. A compound hydrocarbon, following oxygenation is used as a type of reducing agent. In this experiment, the AgCl/Al2O3 catalyst was produced by four different methods, and the differences among their reduction catalysis of NOx were compared. Ethanol was used as a type of reducing agent. X-ray diffraction analysis was performed to study the crystalline structure and scanning electron microscope and transmission electron microscope (TEM) were applied to determine the microindentation. The results indicated that, in the range of 350–400°C, there was no significant difference on the NOx reduction rate; however, there was dispersion at high and low temperature ranges. The size of the AgCl particles was about 20–100 nm.     

不同制备方法对Cu-SSZ-13催化性能的影响

为了考察制备方法对Cu-SSZ-13催化剂在氨选择性催化还原NO_x(NH_3-SCR)中催化性能的影响,使用不同的方法和载体,制备出理化性质有明显差异的3种催化剂(Cu_(3.9)-Na_(0.8)-SSZ-13、Cu_(5.1)-H-SSZ-13和Cu_(4.0)-Na_(4.0)-SSZ-13),并考察3种催化剂的水热稳定性和抗硫中毒性能.结果表明,由于具有适宜的Cu负载量,并且Cu物种的稳定性极高,一步合成法制备的Cu_(3.9)-Na_(0.8)-SSZ-13催化剂的水热稳定性优于液相离子交换法制备的两种催化剂.而以H-SSZ-13为载体,液相离子交换法负载Cu物种制备的Cu_(5.1)-H-SSZ-13催化剂具有最优的抗硫中毒能力,这与其较多的酸性位有关.因此,含有较多酸性位并且活性物种稳定性高是制备水热稳定性和抗硫中毒能力较优的Cu-SSZ-13催化剂的关键.     

铁基催化剂的微波水热处理对其SCR脱硝性能的影响

利用微波对共沉淀制备的铁铈钛复合氧化物催化剂前驱体进行水热处理,探讨了微波水热处理对铁基催化剂低温SCR脱硝性能的优化;并对微波水热处理条件的影响进行了正交分析.结果表明:对铁基催化剂前驱体进行微波水热处理,可提高其低温SCR脱硝性能,使其脱硝温度窗口向低温偏移;且微波水热处理的低温优化效果与催化剂中Fe/Ti摩尔比密切相关,Fe/Ti摩尔比越小,微波水热处理的低温优化越强;微波加热方式和微波辐射时间会影响微波水热处理对铁基催化剂SCR脱硝性能的低温优化;在相同微波辐射时间条件下,当P30逐渐变为P80,微波水热处理对铁基催化剂低温SCR脱硝的促进作用降低;在P30条件下,微波辐射15min使铁基催化剂具有最佳低温SCR脱硝活性.     

Effect of SO2 on the performance of Ag-Pd/Al2O3 for the selective catalytic reduction of NOx with C2H5OH

The influence of SO2 on the performance of Ag-Pd/Al2O3 for the selective catalytic reduction （SCR） of NOx with C2H5OH was investigated experimentally. The activity test results suggest that Ag-Pd/Al2O3 shows a small activity loss in the presence of SO2 when using C2H5OH as a reductant. In situ DRIFTS spectra show that the activity loss originates from the formation of surface sulphate species on the Ag-Pd/Al2O3. The surface sulphate species formation inhibits the formation of nitrate, whereas hardly changes the partial oxidation of C2H5OH. Compared with the NOx reduction by C3H6, an obvious suppression of the surface sulphate species formation was observed by DRIFTS experiment when using C2H5OH as a reductant. This phenomenon reveals the better catalytic performance and strong SO2 tolerance of Ag-Pd/Al2O3-C2H50H system.     

The balance of acidity and redox capability over modified CeO2 catalyst for the selective catalytic reduction of NO with NH3

The effect of acidity and redox capability over sulfuric acid-modified CeO_2 catalysts were studied for the selective catalytic reduction of NO_x with NH_3(NH_3-SCR). The deposition of sulfate significantly enhanced the catalytic performance over CeO_2. NO_x conversion over4H_2SO_4/CeO_2 at 230–440 °C was higher than 90%. The strong redox capability of CeO_2 could result in unselective NH_3 oxidation and decrease high temperatures catalytic activity and N_2 selectivity. The deposition of sulfate increased the acidity and weakened the redox capability, and then increased the high temperature NO_x conversion and N_2 selectivity. An appropriate level of acidity also promoted the activity at 190–250 °C over ceria-based catalysts, and with further increase in the acidity, the SCR activity decreased slightly. Weak redox capability lowered the low-temperature catalytic activity. Excellent SCR activity requires a balance of acidity and redox capability on the catalysts.     

Highly selective catalytic reduction of NOxby MnOx–CeO2–Al2O3 catalysts prepared by self-propagating high-temperature synthesis

We first present preparation of MnOx–CeO_2–Al_2O_3 catalysts with varying Mn contents through a self-propagating high-temperature synthesis(SHS) method, and studied the application of these catalysts to the selective catalytic reduction of NOxwith NH3(NH_3-SCR).Using the catalyst with 18 wt.% Mn(18 MnCe1Al2), 100% NO conversion was achieved at 200°C and a gas hourly space velocity of 15384 hr-1, and the high-efficiency SCR temperature window, where NO conversion is greater than 90%, was widened to a temperature range of 150–300°C. 18 MnCe1Al2 showed great resistance to SO_2(100 ppm)and H_2O(5%) at 200°C. The catalysts were characterized using X-ray diffraction, X-ray photoelectron spectroscopy, Brunauer–Emmett–Teller(BET) analysis, scanning electron microscopy, Fourier transform infrared spectroscopy, and H_2 temperature programmed reduction. The characterization results showed that the surface atomic concentration of Mn increased with increasing Mn content, which led to synergism between Mn and Ce and improved the activity in the SCR reaction. 18 MnCe1Al2 has an extensive pore structure,with a BET surface area of approximately 135.4 m~2/g, a pore volume of approximately 0.16 cm~3/g, and an average pore diameter of approximately 4.6 nm. The SCR reaction on 18 MnCe1Al2 mainly followed the Eley-Rideal mechanism. The performances of the MnOx–CeO_2–Al_2O_3 catalysts were good, and because of the simplicity of the preparation process,the SHS method is applicable to their industrial-scale manufacture.     

Iron-doped Mn-Ce/TiO2 catalyst for low temperature selective catalytic reduction of NO with NH3

The catalysts of iron-doped Mn-Ce/TiO 2(Fe-Mn-Ce/TiO 2) prepared by sol-gel method were investigated for low temperature selective catalytic reduction(SCR) of NO with NH 3.It was found that the NO conversion over Fe-Mn-Ce/TiO 2 was obviously improved after iron doping compared with that over Mn-Ce/TiO 2.Fe-Mn-Ce/TiO 2 with the molar ratio of Fe/Ti = 0.1 exhibited the highest activity.The results showed that 96.8% NO conversion was obtained over Fe(0.1)-Mn-Ce/TiO 2 at 180°C at a space velocity of 50,000 hr 1.Fe-Mn-Ce/TiO 2 exhibited much higher resistance to H 2 O and SO 2 than that of Mn-Ce/TiO 2.The properties of the catalysts were characterized using X-ray diffraction(XRD),N 2 adsorption,temperature programmed desorption(NH 3-TPD and NOx-TPD),and Xray photoelectron spectroscopy(XPS) techniques.BET,NH3-TPD and NOx-TPD results showed that the specific surface area and NH3 and NOx adsorption capacity of the catalysts increased with iron doping.It was known from XPS analysis that iron valence state on the surface of the catalysts were in Fe3+ state.The doping of iron enhanced the dispersion and oxidation state of Mn and Ce on the surface of the catalysts.The oxygen concentrations on the surface of the catalysts were found to increase after iron doping.Fe-Mn-Ce/TiO2 represented a promising catalyst for low temperature SCR of NO with NH3 in the presence of H2 O and SO2.     

Effect of MoO3 on vanadium based catalysts for the selective catalytic reduction of NOx with NH3 at low temperature

The selective catalytic reduction(SCR) activities of the MoO_3 doped V/WTi catalysts prepared by the incipient wetness impregnation method at low temperature were investigated.The results showed that the addition of MoO_3 could enhance the NO_ xconversion at low temperature and the best SCR activity was obtained when the dosage of MoO_3 reached5 wt.%. The NH3-TPD and DRIFTS experiments indicated that the addition of MoO_3 changed the type and number of acid sites on the surface of catalysts and reaction activities of acid sites were altered at the same time. The redox capacity and amount of active oxygen species got improved for V3Mo5/WTi catalyst, which could be confirmed by the H_2-TPR and transient response experiments. Water vapor inhibited the NO_xconversion at low temperature. Deposition of ammonium sulfate or bisulfate might be main reason for the loss of catalytic activity in the presence of SO_2 at low temperature. Choosing the suitable NH_3/NO ratio and elevation of reaction temperature both could weaken the influence of SO_2 on the SCR activity of the V3Mo5/WTi catalyst. Thermal treatment of the deactivated catalyst at350°C could get the low temperature activity recovered. The decrease of GHSV improved the de NO_x efficiency at low temperature and we speculated that the rational technological process and operation parameters could contribute to the application of this kind of catalysts in real industrial environment.     

Ultrasound-assistant preparation of Cu-SAPO-34 nanocatalyst for selective catalytic reduction of NO by NH3

The influence of the various preparation methods of Cu-SAPO-34 nanocatalysts on the selective catalytic reduction of NO with NH₃ under excess oxygen was studied. Cu-SAPO-34 nanocatalysts were prepared by using four techniques: conventional impregnation (IM), ultrasound-enhanced impregnation (UIM), conventional deposition precipitation (DP) using NaOH and homogeneous deposition precipitation (HDP) using urea. These catalysts were characterized in detail by various techniques such as N₂-sorption, XRD, TEM, H₂-TPR, NH₃-TPD and XPS to understand the catalyst structure, the nature and the dispersed state of the copper species, and the acid sites for NH₃ adsorption. All of the nanocatalysts showed high activities for NO removal. However, the activities were different and followed the sequence of Cu-SAPO-34 (UIM) > Cu-SAPO-34 (HDP) > Cu-SAPO-34 (IM) > Cu-SAPO-34 (DP). Based on the obtained results, it was concluded that the NO conversion on Cu-SAPO-34 nanocatalysts was mainly related to the high reducibility of the isolated Cu^2 + ions and CuO species, the number of the acid sites and the dispersion of CuO species on SAPO-34.     

蜂窝状筛网催化剂上NH_3催化还原NO

 采用蜂窝状筛网载体担载V₂O_5-WO₃-TiO₂研究NH₃选择性催化还原气体中的氧化氮.在催化剂中加入2%的磷酸具有良好的黏结性能.2%(wt.)～4%(wt.)磷酸的加入有助于提高催化剂的催化活性.磷酸的添加量大于4%(wt.)时导致NO转化率降低.同时,磷酸的加入有助于抑制高温下氨氧化反应的发生.壳型法制备的催化剂较体型法具有更高的传质性能,但前者的稳定性和使用寿命不如后者.     

Synergistic effects of Cu species and acidity of Cu-ZSM-5 on catalytic performance for selective catalytic oxidation of n-butylamine

In this work, a series of Cu-ZSM-5 catalysts with different SiO₂/Al₂O₃ ratios(25, 50, 100 and₂00) were synthesized and investigated in n-butylamine catalytic degradation. The n-butylamine can be completely catalytic degradation at 350 °C over all Cu-ZSM-5 catalysts. Moreover, Cu-ZSM-5(25) exhibited the highest selectivity to N₂, exceeding 90% at 350 °C. These samples were investigated in detail by several characterizations to illuminate the ...     

高分散MnOx/SAPO-34催化剂的制备及其低温NH3选择性催化还原NO性能

采用改进的溶胶-凝胶法制备一系列MnO_x/SAPO-34催化剂,考察了各制备参数对催化剂的结构及其低温氨选择性催化还原(NH_3-SCR)脱硝性能的影响,并通过X射线衍射、N_2吸附-脱附、透射电镜、X射线光电子能谱、NH_3程序升温脱附等手段对催化剂进行表征.结果表明,当制备参数为n(乙醇)/n(Mn)=15,n(H_2O)/n(Mn)=20,n(柠檬酸)/n(Mn)=1,Mn负载量为15%(质量分数),催化剂焙烧温度为350℃时,制备的高分散15%-MnO_x/SAPO-34-350℃催化剂具有最佳的低温SCR活性,在空速为45000 h~(-1)的条件下,且反应温度在120～240℃范围时均保持90%以上的NO转化率和接近100%的N_2选择性.MnO_x纳米颗粒高度分散在SAPO-34载体表面,平均粒径约为5.46 nm,纳米颗粒的表面效应使得该催化剂具备较大的比表面积,暴露出大量的活性位点和高活性的MnO_2(110)晶面,同时,高Mn~(4+)比例和更多的化学吸附氧以及适宜的表面酸强度和酸量也是15%-MnO_x/SAPO-34-350℃催化剂呈现最佳低温SCR活性的重要原因.     

低温等离子体改性对Fe2O3/ACF低温选择性催化还原NO的影响

利用N2低温等离子体对过量溶液浸渍法制备的Fe2O3/ACF（活性炭纤维）催化剂进行了改性,运用BET比表面积、扫描电子显微镜（SEM）、X射线衍射光谱（XRD）和傅立叶变换红外光谱（FT\|IR）对催化剂进行表征.同时,对催化剂的NH3选择性催化还原（SCR）NO的催化性能进行了研究.结果表明,活性组分最佳负载量的质量分数为10.3%;N2等离子体改性最优改性电压为6kV,改性时间为3min;随着反应温度的升高,空白ACF上NO转化率先升高再下降,而催化剂上NO转化率呈上升趋势.在NO体积分数1000×10-6、NH3体积分数1000×10-6、O2体积分数5%、空速10040h-1和反应温度240℃的条件下,催化剂3.7%Fe2O3/ACF和10.3%Fe2O3/ACF经N2等离子体改性后,其NO转化率（相对于未改性的）分别提高了16.43%和6.84%.N2等离子体改性催化剂提高了活性组分在ACF上的分散度,增加了ACF表面的含氮官能团,从而提高了催化剂的SCR低温活性.     

Synthesis and kinetics investigation of meso-microporous Cu-SAPO-34 catalysts for the selective catalytic reduction of NO with ammonia

A series of meso-microporous Cu-SAPO-34 catalysts were successfully synthesized by a one-pot hydrothermal crystallization method, and these catalysts exhibited excellent NH_3-SCR performance at low temperature. Their structure and physic chemical properties were characterized by means of X-ray diffraction patterns(XRD), Scanning electron microscopy(SEM), Transmission electron microscopy(TEM), N_2 sorption-desorption, nuclear magnetic resonance(NMR), Inductively Coupled Plasma-Atomic Emission spectrometer(ICP-AES), X-ray absorption spectroscopy(XPS),Temperature-programmed desorption of ammonia(NH_3-TPD), Ultraviolet visible diffuse reflectance spectroscopy(UV-Vis DRS) and Temperature programmed reduction(TPR).The analysis results indicate that the high activities of Cu-SAPO-34 catalysts could be attributed to the enhancement of redox property, the formation of mesopores and the more acid sites. Furthermore, the kinetic results verify that the formation of mesopores remarkably reduces diffusion resistance and then improves the accessibility of reactants to catalytically active sites. The 1.0-Cu-SAPO-34 catalyst exhibited the high NO conversion( 90%) among the wide activity temperature window in the range of 150–425℃.     

VxMn(4 − x)Mo3Ce3/Ti catalysts for selective catalytic reduction of NO by NH3

A series of vanadium based catalysts(VxMn(4-x)Mo3Ce3/Ti) with different vanadium(x wt.%) and manganese((4-x) wt.%) contents have been prepared by the wet impregnation method and investigated for selective catalytic reduction(SCR) of NO_x by NH_3 in the presence of 8 vol.% H_2O and 500 ppm V SO_2.The physicochemical characteristics of the catalysts were thoroughly characterized.The SCR of NO_x by NH_3(NH_3-SCR) activity, especially the low-temperature activity, significantly increased with increasing V_2O_5 content in the catalyst until the V_2O_5 content reached 1.5 wt.%, which corresponds well with the redox properties of the catalyst.All of the metal oxides were well dispersed and strongly interacted with each other on the catalyst surface.V mainly exists in the V~(5+)state in the catalysts.The strong synergistic effect between the vanadium and cerium species led to formation of more Ce~(3+)species, and that between the vanadium and manganese species contributed to formation of more manganese species with low valences.All of the catalysts exhibited strong acidity, while the redox properties determined the NH_3-SCR activity, especially the low-temperature activity.H_2O and SO_2 had severe inhibiting effects on the activity of V1.5Mn2.5Mo3Ce3/Ti.However, good H_2O and SO_2 resistance and high NO_x conversion by V1.5Mn2.5Mo3Ce3/Ti could be achieved in the presence of SO_2 and almost no decline was observed in a long-term test at 275℃ for 168 hr in the presence of SO_2 and H_2O, which can be attributed to the sulfate species formed on the catalyst surface.     

Fe2O3 particles as superior catalysts for low temperature selective catalytic reduction of NO with NH3

Fe203 particle catalysts were experimentally studied in the low temperature selective catalytic reduction （SCR） of NO with NH3. The effects of reaction temperature, oxygen concentration, [NH3]/[NO] molar ratio and residence time on SCR activity were studied. It was found that Fe203 catalysts had high activity for the SCR of NO with NH3 in a broad temperature range of 150-270℃, and more than 95% NO conversion was obtained at 180℃ when the molar ratio [NH3]/[NO] = 1, the residence time was 0.48 seconds and 02 volume fraction was 3%. In addition, the effect of SO2 on SCR catalytic activity was also investigated at the temperature of 180℃. The results showed that deactivation of the Fe2O3 particles occurred due to the presence of SO2 and the NO conversion decreased from 99.2% to 58% in 240 min, since SO2 gradually decreased the catalytic activity of the catalysts. In addition, X-ray diffraction, Thermogravimetric analysis and Fourier transform infrared spectroscopy were used to characterize the fresh and deactivated Fe2O3 catalysts. The results showed that the deactivation caused by SO2 was due to the formation of metal sulfates and ammonium sulfates on the catalyst surface during the de-NO reaction, which could cause pore plugging and result in suppression of the catalytic activity.     

Mn-CeOx/Ti-PILCs for selective catalytic reduction of NO with NH3 at low temperature

Titanium-pillared clays (Ti-PILCs) were obtained by different ways from TiCl₄, Ti(OC₃H₇)₄ and TiOSO₄, respectively. Mn-CeO_x/Ti-PILCs were then prepared and their activities of selective catalytic reduction (SCR) of NO with NH₃ at low-temperature were evaluated. Mn-CeO_x/Ti-PILCs were characterized by X-ray diffraction, N₂ adsorption, Fourier transform infrared spectroscopy, thermal analysis, temperature-programmed desorption of ammonia and H₂-temperature-programmed reduction. It was found that Ti-pillar tend to be helpful for the enlargement of surface area, pore volume, acidity and the enhancement of thermal stability for Mn-CeO_x/Ti-PILCs. Mn-CeO_x/Ti-PILCs catalysts were active for the SCR of NO. Among three resultant Mn-CeO_x/Ti-PILCs, the catalyst from TiOSO₄ showed the highest activity with 98% NO conversion at 220℃, it also exhibited good resistance to H₂O and SO₂ in flue gas. The catalyst from TiCl₄ exhibited the lowest activity due to the unsuccessful pillaring process.     

The selective catalytic reduction of NO over Ce0.3TiOx-supported metal oxide catalysts

A Ce_(0.3)TiO_xoxide carrier was synthesized via a sol–gel process,and Ce_(0.3)TiO_xsupported metal(M=Cd,Mn,Fe,W,Mo)oxide catalysts were prepared by the method of incipient-wetness impregnation.The catalysts were characterized by means of X-ray diffraction(XRD),Brunauer–Emmett–Teller(BET)analysis,scanning electron microscopy(SEM),transmission electron microscopy(TEM),Fourier transform infrared(FT–IR)spectroscopy,UV–Visdiffusereflectancespectroscopy(UV–VisDRS),and Temperature-programmed reduction with H_2(H_2-TPR).The catalytic activities for de-NO_(x )were evaluated by the NH_3-SCR reaction.Among all the catalysts tested,the 2 wt.%Cd/Ce_(0.3)TiO_xcatalyst exhibited the best NH_3-SCR performance,with a wide temperature window of 250–450°C for NO conversion above 90%.Moreover,the catalyst showed N_2 selectivity greater than 99%from 200 to 450°C.