金属改性对SAPO-34低温还原NO性能的影响

采用浸渍法制备金属改性SAPO-34分子筛催化剂,分析比较了不同单金属（Cu或Co）及不同比例双金属（Cu：Co=1：1、3：1、5：1,质量比）改性催化剂对NO的催化还原性能,评价了不同催化剂的N₂选择性,并采用扫描电子显微镜（SEM）、比表面积测试、X射线衍射分析（XRD）、NH₃-程序升温脱附（NH₃-TPD）等表征手段对催化剂的物化性能进行了分析.结果表明,单金属Cu改性催化剂具有较宽的温度区间,在250~450℃范围内NO的转化率始终保持在100%;双金属改性使NO转化率保持为100%的最低温度下降了25~50℃,显著拓宽了低温段窗口,其中,Cu₃Co₁/SAPO-34催化剂的低温催化还原性能最好,200℃即可实现100%的NO转化率,175℃下的转化率也高达80%以上.Cu-Co双金属改性SAPO-34分子筛催化剂具有优异的低温催化还原NO性能,具有在机动车尾气、工业废气的低温脱硝治理领域应用的潜力.     

焙烧温度对Fe2O3/SAPO-34催化剂低温NH3选择性催化还原NO性能的影响

采用尿素沉淀法制备了一系列Fe_2O_3/SAPO-34催化剂,考察了催化剂焙烧温度(200、300、400、500℃)对低温NH_3选择性催化还原(NH_3-SCR)NO性能的影响,并利用X射线衍射(XRD)、N_2吸附-脱附、原子吸收光谱(AAS)、场发射扫描电镜(FE-SEM)、X射线光电子能谱(XPS)、H_2程序升温还原(H_2-TPR)、NH_3程序升温脱附(NH_3-TPD)等多种手段对催化剂的表面结构和物理化学性质进行表征分析.XRD和FE-SEM分析表明,在较低的焙烧温度(400℃)下,铁物种能够高度均匀地负载在SAPO-34表面上.NH_3-TPD和H_2-TPR分析表明,高分散状态的Fe_2O_3使催化剂暴露出更多的强酸位和活性位,有利于提高催化剂的NH_3吸附和活化能力及氧化还原性能,从而使催化剂呈现出更高的低温SCR活性.BET和XPS分析表明,在较低的焙烧温度下,Fe_2O_3/SAPO-34催化剂具有更大的比表面积和更高的化学吸附氧比例,促进NO氧化为中间产物NO_2,从而加快低温SCR反应的进行.活性测试结果表明,300℃焙烧的Fe_2O_3/SAPO-34催化剂具有最佳的低温活性和较强的抗硫抗水性能,在空速为40000 h~(-1)的条件下,且反应温度为190~240℃时,NO转化率达90%以上且N_2选择性接近100%.     

Structures and catalytic performances of Me/SAPO-34 (Me = Mn, Ni, Co) catalysts for low-tem perature SCR of NOx by ammonia

Me/SAPO-34 (Me = Mn, Ni, Co) series of catalysts were prepared by a wetness impregnation method and investigated for the selective catalytic reduction of nitrogen oxides with ammonia (NH₃-SCR). Among them, Mn/SAPO-34 catalyst was found as the most promising candidate based on its superior low-temperature activity. The catalysts were characterized by X-ray diffraction (XRD), transmission electron microscopy images (TEM), nuclear magnetic resonance (NMR), X-ray photoelectron spectroscopy (XPS), temperature programmed reduction and desorption (TPR and TPD), and diffuse reflectance infrared Fourier transformed spectroscopy (DRIFTS) of NH₃/NO_x adsorption. Mn/SAPO-34 is obviously different from Ni/SAPO-34 and Co/SAPO-34 in the active species state and distribution. Surface MnO_x species which play an essential role in NO oxidation and NO₂ adsorption, act as better active sites than nickel and cobalt mostly in the form of the aluminates and silicates.     

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.     

汽车尾气净化催化剂Ag/SAPO-34选择性催化还原NO

评价了Ag/SAPO-34分子筛催化剂选择性还原NO的活性,并运用漫反射红外光谱原位研究NO在Ag/SAPO-34催化剂上的选择性催化还原机理.结果表明Ag/SAPO-34有良好的低温活性,在氧气浓度为3.6%和温度为573K～673K时NO还原成N2的转化率达70%;催化剂活性随C3H6浓度的增加而升高,随空速的增加而稍有下降.基于漫反射红外光谱,认为反应机理为:NO、丙烯和氧反应,在Ag/SAPO-34催化剂上生成吸附的有机-氮氧化物,再由这些吸附物种分解成N₂,催化还原的关键是形成有机-氮氧化物中间体.氧的作用是充分促进丙烯活化以及增加NO_x吸附态含量,并且氧的存在是有效产生一系列中间物不可缺少的条件.     

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℃.     

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.     

Optimizing the crystallinity and acidity of H-SAPO-34 by fluoride for synthesizing Cu/SAPO-34 NH3-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), N₂ physisorption, temperature-programmed desorption of NH₃ (NH₃-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 NH₃ (NH₃-SCR) reaction due to the enhanced acidity of the zeolite and the improved dispersion of copper species.     

环境因素对海洋动物Na+-K+-ATPase的影响概述

概述了Ｎａ＋－Ｋ＋－ＡＴＰａｓｅ的一般性质以及各种环境因子对其的影响情况和作用机理，并对Ｎａ＋－Ｋ＋－ＡＴＰａｓｅ活性作为环境污染指示物的可行性进行了初步探讨     

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.     

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 ...     

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.     

以飞灰为载体的金属氧化物催化剂脱硝研究

以飞灰作为催化剂的载体 ,担载Fe、Cu、V、Ni等过渡金属作为活性成分制成脱硝催化剂 .对飞灰作为载体的催化剂进行了各种表征分析 ,考察了催化剂的制备条件对脱硝效率的影响 .利用固定床反应装置进行了催化脱硝实验研究 ,结果发现 ,飞灰作为脱硝催化剂的载体是可行的 ,其中担载Cu作为活性成分时脱硝效率最好 ,在温度为 2 70℃时NO的转化率达90 %以上 .最后 ,对活性炭和页岩灰作载体时的催化脱硝特性进行了对比研究 ,发现飞灰的催化活性仅次于活性炭 ,而页岩灰的活性最差 .     

Cu/Cu_2O材料的制备及形貌调控研究

目的一步制备和调控Cu/Cu_2O材料。方法采用水热法合成Cu/Cu_2O材料,通过改变反应时间、温度,原料投料量以及乙醇和水混合溶液中溶剂比等参数来调控Cu/Cu_2O复合材料的晶体形貌和Cu含量。结果增加氨水和甲酸使用量会明显提升Cu/Cu_2O复合材料中的Cu含量,硝酸铜和混合溶液(乙醇+水)中水量增加会使Cu/Cu_2O复合材料中Cu含量减少,而反应时间和反应温度均不会使复合材料中Cu量发生变化。氨水和甲酸使用量的增加,会使样品从菜花状、正八面体或十二面体向类球状转变。而硝酸铜和混合溶液(乙醇+水)中水量增加恰好使得样品形貌向相反方向变化。另外,反应温度过高会使得晶体向正八面体转变并且逐渐出现孔隙。结论通过改变样品合成参数可成功调控Cu/Cu_2O复合材料中Cu含量和形貌。     

Fe/Cu体系湿式催化氧化一步高效脱除H2S新方法研究

提出了Fe/Cu体系室温湿式催化氧化一步高效脱除H2S废气的新方法,阐述了反应机理、实验装置和工艺流程;考察了Fe3+、Cu2+浓度和H2S入口浓度对H2S脱除效率的影响及Fe3+、H+与添加剂NaCl浓度对CuS氧化浸出的影响,分析了Fe3+、Cu2+、H+浓度和废气中O2含量对fe3+、Cu2+再生的影响;并进行了综合实验.结果表明,当废气中O2体积分数为5%时,新方法中含40g·L-1Cu2+及80g·L-1Fe3+的吸收体系即能对体积分数为1000×10-6的H2S废气100%稳定脱硫,体系除消耗O外,过程不消耗任何原料,不产生二次污染,体系无降解问题.     

Cu/TiO_2/SiO_2纳米复合薄膜光催化降解氨气性能的研究

采用溶胶-凝胶结合γ-射线辐射法制备了Cu/TiO2/SiO2纳米介孔复合薄膜。X-射线衍射(XRD),透射电子显微镜(TEM),紫外-可见光谱(UV-vis)及X-射线光电子能谱(XPS)表征显示单质金属铜与锐钛矿型TiO2纳米粒子较均匀地分布在非晶SiO2介孔基体的孔洞之中。光催化降解氨气的实验结果表明该三元复合薄膜具有良好的光催化性能,与未掺杂铜的TiO2/SiO2二元复合薄膜相比,铜纳米粒子的掺入可将其光催化性能提高18%以上。     

铜离子对螺旋藻生长的影响

主要研究了不同浓度的Cu^2＋对螺旋藻生长的影响,结果表明：Cu^2＋浓度为0．079mg／L时对螺旋藻的生长具有明显的促进作用,当浓度大于0．395mg／L时则对螺旋藻的生长产生抑制作用,而且抑制作用随着铜离子浓度的增加而增强;铜离子对螺旋藻的完全抑制质量浓度为39．50mg／L。     

壳聚糖/聚氨酯多孔材料对Cu~(2+)、Cd~(2+)的吸附研究

将壳聚糖、聚醚多元醇、甲苯二异氰酸酯混合发泡,制备了壳聚糖/聚氨酯(Cs/PU)多孔复合材料,利用原子吸收光谱研究了Cs/PU对水中Cu2+、Cd2+的吸附能力。结果表明:在28℃条件下,当吸附时间为30min,溶液pH=4～5时,Cu2+的最高去除率为96.67%,溶液pH=6～7时,Cd2+的去除率为95.67%。Cd2+、Cu2+的饱和吸附率容量分别为28.78mg/g和25.32mg/g。两种金属离子共存时,Cs/PU对Cu2+的选择性大于Cd2+。     

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.     

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 NH_3.The kinetics of the SCR reaction in the presence of O_2 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,O_2 and NH_3 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 N_2 and H_2O.Gaseous O_2 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 NH_3.