低温磁性铁基SCR烟气脱硝的实验研究

在流化床反应器中,以磁性铁氧化物(Fe3O4、γ-Fe2O3)颗粒为床料,氨为还原剂,进行了中低温SCR烟气脱硝实验研究,然后对反应辅加磁场,初步研究磁场对磁性γ-Fe2O3催化剂SCR脱硝的影响,并对床料进行了XRD分析.结果表明,Fe3O4的SCR活性较差,γ-Fe2O3的SCR活性较佳,在250℃其催化脱硝效率能达到90%,但在250℃以上Fe2O3会对氨的氧化起作用,因而在250℃及以下的邻近温度区间是最佳催化温度区间.此外,在150~290℃,外加磁场能促进γ-Fe2O3对NO的吸附,提高脱硝效率,使250℃时的脱硝效率达到95%左右,但在290℃以上,则会降低脱硝效率.为了抑制氨的氧化,发挥磁场对γ-Fe2O3脱硝的作用,适合在200~250℃低温区间内采用γ-Fe2O3催化剂进行SCR脱硝.     

Nano-sized alumina supported palladium catalysts for methane combustion with excellent thermal stability

Pd/Al₂O₃ catalysts supported on Al₂O₃ of different particle sizes were synthesized and applied in methane combustion. These catalysts were systematically characterized by Brunauer-Emmett-Teller (BET), X-ray diffraction (XRD), high resolution-transmission electron microscopy (HR-TEM), high-angle annular dark field-scanning transmission electron microscopy (HAADF-STEM), H₂-temperature-programmed reduction (H₂-TPR), O₂-temperature-programmed oxidation (O₂-TPO), X-ray photoelectron spectroscopy (XPS), and X-ray absorption fine structure (XAFS). The characterization results indicated that nano-sized Al₂O₃ enabled the uniform dispersion of palladium nanoparticles, thus contributing to the excellent catalytic performance of these nano-sized Pd/Al₂O₃ catalysts. Among them, Pd/Al₂O₃-nano-10 (Pd/Al₂O₃ supported by alumina with an average particle size of 10 nm) showed superior catalytic activity and stability for methane oxidation under harsh practical conditions. It maintained excellent catalytic performance for methane oxidation for 50 hr and remained stable even after harsh hydrothermal aging in 10 vol.% steam at 800°C for 16 hr. Characterization results revealed that the strong metal-support interactions and physical barriers provided by Al₂O₃-nano-10 suppressed the coalescence ripening of palladium species, and thus contributed to the superior sintering resistance of the Pd/Al₂O₃-nano-10 catalyst.     

Complete catalytic oxidation of o-xylene over Ce02 nanocubes

The activities of CeO2 nanocubes calcined at different temperatures were tested for catalytic oxidation of o-xylene. Using CeO2 nanocubes as catalysts, complete catalytic oxidation of o-xylene was achieved below 210℃. The CeO2 nanomaterials were characterized by means of BET, X-ray diffraction (XRD), transmission electron microscopy (TEM), and high-resolution transmission electron microscopy (HRTEM). From the TEM images, all Ce02 nanocubes displayed cubic morphology irrespective of calcination temperature. The HRTEM images revealed that these nanocubes were enclosed by reactive {001}planes, which may contribute to the intrinsically catalytic property of o-xylene oxidation. The higher activity of Ce02 nanocubes calcined at 550℃ than those calcined at above 550℃ was attributed to their smaller crystallite size and larger surface area. The influences of reaction conditions were also studied, which found that a higher reaction temperature was necessary for complete catalytic oxidation of o-xylene at higher weight hourly space velocity (WHSV) and o-xylene concentration.     

Complete catalytic oxidation of o-xylene over CeO2 nanocubes

The activities of CeO2 nanocubes calcined at di erent temperatures were tested for catalytic oxidation of o-xylene. Using CeO2 nanocubes as catalysts, complete catalytic oxidation of o-xylene was achieved below 210°C. The CeO2 nanomaterials were characterized by means of BET, X-ray di raction (XRD), transmission electron microscopy (TEM), and high-resolution transmission electron microscopy (HRTEM). From the TEM images, all CeO2 nanocubes displayed cubic morphology irrespective of calcination temperature. The HRTEM images revealed that these nanocubes were enclosed by reactive f001g planes, which may contribute to the intrinsically catalytic property of o-xylene oxidation. The higher activity of CeO2 nanocubes calcined at 550°C than those calcined at above 550°C was attributed to their smaller crystallite size and larger surface area. The influences of reaction conditions were also studied, which found that a higher reaction temperature was necessary for complete catalytic oxidation of o-xylene at higher weight hourly space velocity (WHSV) and o-xylene concentration.     

Photocatalytic performance of TiO2 catalysts modified by H3PW12O40, ZrO2 and CeO2

The binary composite photo-catalysts CeO2/TiO2, ZrO2/TiO2 and the ternary composite photo-catalysts H3PW12O40-CeO2/TiO2,H2PW12O40-ZrO2/TiO2 were prepared by sol-gel method. The catalysts were characterized by thermogravimetric-differential thermal analysis (TG-DTA), scanning electron microscopy (SEM) and X-ray diffraction (XRD). The photocatalyfic elimination of methanol was used as model reaction to evaluate the photocatalytic activity of the composite catalysts under ultraviolet light irradiation. The effects of doped content, activation temperature, time, initial concentration of methanol and gas flow rate on the catalytic activity were investigated. The results showed that after doping a certain amount of CeO2 and ZrO2, crystaniTation process of TiO2 was restrained, particles of catalysts are smaller and more uniform. Doping ZrO2 not only significantly improved the catalytic activity, but also increased thermal stability. Doping H3PW12O40 also enhanced the catalytic activity. The catalytic activities of binary and ternary composite photocatalysts were significantly higher than tin-doped TiO2. The dynamics law of photocatalytic reaction over the binary CeO2/TiO2 and ZrO2/TiO2 catalysts has been studied. The activation energy 15.627 and 15.631 kJ/mol and pre-exponential factors 0.5176 and 0.9899 s-1 over each corresponding catalyst were obtained. This reaction accords to the first order dynamics law.     

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.     

Characterization of metal doped-titanium dioxide and behaviors on photocatalytic oxidation of nitrogen oxides

A series of nanosized ion-doped TiO_2 catalysts with different ion content(between 0.1 at.% and 1.0 at.%) have been prepared by wet impregnation method and investigated with respect to their behavior for UV photocatalytic oxidation of nitric oxide.The catalytic activity was correlated with structural,electronic and surface examinations of the catalysts using X-ray diffraction analysis (XRD),ultraviolet-visible(UV-Vis)absorption spectroscopy,transmission electron microscopy(TEM),energy disperse spectrometer (EDS)and high resolution-transmission electron microscopy (HR-TEM) techniques.An enhancement of the photocatalytic activity was observed for Zn~(2 ) doping catalyst ranged from 0.1 at.% to 1.0 at.% which was attributed to the lengthened lifetime of electrons and holes.The improvement in photocatalytic activity could be also observed with the low doping concentration of Cr~(3 )(0.1 at.%). However,the doping of Fe~(3 ),Mo~(6 ),Mn~(2 ) and the high doping concentration of Cr~(3 ) had no contribution to photocatalytic activity of nitric oxide.     

Preparation of birnessite-supported Pt nanoparticles and their application in catalytic oxidation of formaldehyde

Flaky and nanospherical birnessite and birnessite-supported Pt catalysts were successfully prepared and characterized by means of X-ray diffraction (XRD), transmission electron microscopy (TEM), energy dispersive spectroscopy (EDS) and N₂ adsorption-desorption. Effects of the birnessite morphology and Pt reduction method on the catalytic activity for the complete oxidation of formaldehyde (HCHO) were investigated. It was found that flaky birnessite exhibited higher catalytic activity than nanospherical birnessite. The promoting effect of Pt on the birnessite catalyst indicated that the reduction method of the Pt precursor greatly influenced the catalytic performance. Flaky birnessite-supported Pt nanoparticles reduced by KBH₄ showed the highest catalytic activity and could completely oxidize HCHO into CO₂ and H₂O at 50℃, whereas the sample reduced using H₂-plasma showed lower activity for HCHO oxidation. The differences in catalytic activity of these materials were jointly attributed to the effects of pore structure, surface active sites exposed to HCHO and the dispersion of Pt nanoparticles.     

Ag-Al2O3催化剂选择性催化还原稀薄燃烧NOx的研究

本研究主要考察了丙烯为还原剂 ,溶胶 凝胶和共沉淀两种方法制备的Ag Al2 O3催化剂的活性 ,实验结果表明Ag(5 ) Al2 O3(SG)催化剂具有最高的活性。同时详细考察了C3H6 浓度、NO浓度和空速等因素对Ag(5 ) Al2 O3(SG)催化剂活性的影响 ,实验结果表明该催化剂在高空速条件下仍然具有良好的性能。此外 ,还考察了乙烯、丙烷和辛烷为还原剂 ,Ag(5 ) Al2 O3(SG)催化剂的活性 ,实验结果表明以辛烷为还原剂 ,该催化剂还原NOx 的活性 ,特别是低温活性明显提高     

由贵金属取代的钙钛矿催化剂对碳烟的催化性能

用柠檬酸法制备了不同贵金属取代的钙钛矿LaCo0.96X0.04O3(X为Pt、Pd、Rh、Au、Ag)催化剂,用热重法测试了催化剂对碳烟的催化活性,采用程序升温还原法(H2-TPR)、X-射线衍射仪(XRD)、能量谱仪(EDS)和红外光谱(FTIR)对催化剂进行了测试.结果表明,催化剂LaCo0.96Ag0.04O3催化活性最高,起燃温度为449℃,远低于LaCoO3的504℃;各贵金属取代的钙钛矿LaCoO3的TPR还原峰变化各异;XRD特征峰的衍射角向高角度偏移,说明各贵金属进入了钙钛矿结构相;能谱图显示各贵金属进入钙钛矿相的量不同.     

Effect of pretreatment on Pd/Al2O3 catalyst for catalytic oxidation of o-xylene at low temperature

The effect of pretreatment on Pd/Al₂O₃ catalysts for the catalytic oxidation of o-xylene at low temperature was studied by changing the pretreatment and testing conditions. The fresh and pretreated Pd/Al₂O₃ catalysts were characterized by transmission electron microscopy (TEM), X-ray photoelectron spectroscopy (XPS) and X-ray diffraction (XRD). The results showed that the pretreatment dramatically changed the Pd/PdO ratio and then significantly affected the Pd/Al₂O₃ activity; while the pretreatment had not much influence on Pd particle size. The Pd/Al₂O₃ pre-reduced at 300℃/400℃, which has fully reduced Pd species, showed the highest activity; while the fresh Pd/Al₂O₃, which has fully oxidized Pd species, presented the worst performance, indicating the Pd chemical state plays an important role in the catalytic activity for the o-xylene oxidation. It is concluded that metallic Pd is the active species on the Pd/Al₂O₃ catalyst for the catalytic oxidation of o-xylene at low temperature.     

低温等离子体结合锰基催化剂去除乙酸乙酯的研究

利用固态法和溶胶-凝胶法分别制备了钙钛矿（LaMnO₃）和八面体分子筛（OMS）两种锰基催化剂,在不同工况（输入电压、初始浓度、停留时间和催化剂放置量）条件下考察了等离子体催化对乙酸乙酯的降解特性.结果发现,锰基催化剂的加入显著提高了乙酸乙酯的去除率,减少了副产物的生成,并且OMS的催化活性高于LaMnO₃;此外,乙酸乙酯去除率随着电压的升高而增加,随着污染物初始浓度的增大而减少,并随停留时间的增长而变大;催化剂放置量为0.2 g时催化效果最佳.OMS催化剂在等离子体催化长期运行过程中表现出较好的稳定性.基于X射线衍射（XRD）、X射线光电子能谱（XPS）、H₂程序升温还原（H₂-TPR）、比表面积测试（BET）、扫描电子显微镜（SEM）、透射电子显微镜（TEM）等手段对锰基催化剂物理化学性质的分析表明,OMS具有较高的催化活性主要归功于其拥有更高比例的Mn⁴⁺/（Mn³⁺+Mn⁴⁺）和吸附氧（O_ads）/晶格氧（O_latt）.     

Mechanism and catalytic performance for direct dimethyl ether synthesis by CO2 hydrogenation over CuZnZr/ferrierite hybrid catalyst

Direct synthesis of dimethyl ether(DME) by CO_2 hydrogenation has been investigated over three hybrid catalysts prepared by different methods:co-precipitation,sol-gel,and solid grinding to produce mixed Cu,ZnO,ZrO_2 catalysts that were physically mixed with a commercial ferrierite(FER) zeolite.The catalysts were characterized by N_2 physisorption,X-ray diffraction(XRD),transmission electron microscopy(TEM),X-ray photoelectron spectroscopy(XPS),temperature programmed desorption of CO_2(CO_2-TPD),temperature programmed desorption of NH_3(NH_3-TPD),and temperature programmed H2 reduction(H_2-TPR).The results demonstrate that smaller CuO and Cu crystallite sizes resulting in better dispersion of the active phases,higher surface area,and lower reduction temperature are all favorable for catalytic activity.The reaction mechanism has been studied using in situ diffuse reflectance infrared Fourier transform spectroscopy(DRIFTS).Methanol appears to be formed via the bidentate-formate(b-HCOO) species undergoing stepwise hydrogenation,while DME formation occurs from methanol dehydration and reaction of two surface methoxy groups.     

复合纳米Fe_3O_4的制备及其控磷效能的研究

采用氧化沉淀法在羧甲基纤维素(CMC)体系中制备了以纳米Fe3O4为核心,外包覆羧甲基纤维素的复合纳米Fe3O4.对比研究了复合纳米Fe3O4和微米Fe3O4对水中磷的吸附以及对土壤中磷的固化,并考察了添加纤维素酶在此过程中所起的作用.结果表明,在水中微米Fe3O4的平衡吸附量为3.2 mg/g,而复合纳米Fe3O4为2.1 mg/g.当将纤维素酶(用以降解包覆在氧化铁表面的羧甲基纤维素)添加到复合纳米Fe3O4吸附磷的溶液中,复合纳米Fe3O4的除磷效率(86%)接近于微米Fe3O4(90%),说明羧甲基纤维素的存在减弱了复合纳米Fe3O4的吸附能力.在土柱实验中,将2种Fe3O4悬浊液注入到10 cm高的土壤柱中,72%的复合纳米Fe3O4穿过土壤柱溢出,而微米Fe3O4完全滞留在土壤柱中没有溢出.原始土壤的固磷率为30%,注入复合纳米Fe3O4的土壤固磷率达到45%,而将纤维素酶和复合纳米Fe3O4一起注入土壤中固磷效率提高到74%.     

纳米CeO2催化氧化甲苯的形貌效应研究

采用水热法合成CeO2纳米棒、纳米颗粒和纳米立方体,利用XRD、BET-N2、TEM/HRTEM、Raman、O2-TPD和H2-TPR等表征手段进行表征,并利用连续流固定床反应法研究各催化剂对甲苯的催化氧化性能.结果表明,CeO2纳米棒因具有高比表面积和细颗粒尺寸,且表面主要暴露高活性的{100}/{110}晶面,拥有更多的氧空位和高活性氧物种,因此,催化活性最高,CeO2纳米颗粒次之,立方体最低.原位红外甲苯催化氧化机理分析进一步表明,CeO2纳米颗粒和纳米立方体上生成的羧酸盐物质难以进一步深度氧化,而纳米棒能在贫氧和低温条件下诱导甲苯的完全氧化和产物脱附,使甲苯得以快速降解.     

铁、锌、铁酸锌掺杂对纳米级二氧化钛光催化降解罗丹明B活性的影响

通过溶胶 凝胶法合成了掺杂Fe3+ 、Zn2 + 、ZnFe2 O4的纳米级TiO2 ,并进行了XRD、TEM表征 ,对罗丹明B的光催化实验表明 ,ZnFe2 O4的掺杂能明显提高TiO2 的光催化活性 ,而Zn2 + 的掺杂对TiO2 的光催化活性影响不大 ,Fe3+ 的掺杂则使TiO2 的光催化活性降低。     

Size effect of Pt nanoparticles in acid-assisted soot oxidation in the presence of NO

Pt/Al₂O₃ catalysts with mean Pt particle size ranged from 2.7 to 7.1 nm were synthesized by chemical reduction method, and the sulfated counterparts were prepared by impregnation of sulfuric acid. The turnover frequency of platinum for soot oxidation under loose contact conditions in a feed flow containing NO and O₂ are positively correlated with the size of platinum. The sulfated Pt/Al₂O₃ exhibits higher catalytic activity for soot oxidation in the presence of NO despite their reduced ability for NO₂ production. Such a contradiction is more significant for those catalysts with smaller platinum particles. Herein, the catalysts were characterized by X-ray diffraction (XRD), Brunauer-Emmett-Teller (BET), transmission electron microscopy (TEM), inductive coupled plasma (ICP) emission spectrometry, CO chemisorption, thermogravimetric analysis (TGA), NH₃ temperature-programmed desorption (NH₃-TPD), NO temperature-programmed oxidation (TPO) and NO_x temperature-programmed desorption (TPD). Possible effect of Pt particle size for the catalytic oxidation of soot in the presence of NO was presented based primarily on the promoted NO₂ transfer efficiency onto the soot pushed by the acidic catalysts.     

治理催化超临界水氧化处理1,5-萘二磺酸

采用Mn2O3γAl2O3和V2O5γAl2O3为催化剂,在一连续流固定床反应器中进行了超临界水氧化1,5萘二磺酸实验。实验结果表明,在380～440℃,24MPa条件下,Mn2O3γAl2O3和V2O5γAl2O3催化剂对1,5萘二磺酸的氧化降解具有显著的促进作用,TOC去除率达到90%以上;催化剂的催化效果随反应温度的升高而增强,随pH值的降低而增强,随停留时间的延长先增强后趋于平缓。     

易挥发有毒化合物催化燃烧试验

在富氧条件下以2.0% Ru/Al₂O₃和2.0% Ru/AC(AC为活性炭)为催化剂,在固定床反应装置上研究了甲醇、氨、甲苯的催化氧化活性及反应动力学. 结果表明,Ru/Al₂O₃对3种反应物的催化活性比Ru/AC高,3种反应物的反应活性顺序为甲醇>氨>甲苯,其去除率随反应物浓度的增加呈先增大后减小的趋势. 反应的活化能(Ea)测定结果为甲醇<氨<甲苯. 比表面积检测(BET)和透射电镜(TEM)结果显示,Ru/Al₂O₃与Ru/AC的孔体积(0.54 mL/g)近似相等,而其孔径分别为9.3和2.3 nm;在大孔径的氧化铝上Ru以极细的粒径(<3 nm)形成高度分散体系,在活性炭上Ru则以较大颗粒(4～10 nm)位于活性炭表面,Ru的粒径细化及形成高分散体系可能是Ru/Al₂O₃的催化活性高于Ru/AC的主要原因.      

Pure and Mg-doped self-assembled ZnO nano-particles for the enhanced photocatalytic degradation of 4-chlorophenol

A novel self-assembled pure and Mg doped ZnO nano-particles （NPs） were successfully synthesized by a simple low temperature co-precipitation method. The prepared photocatalysts were characterized by X-ray diffraction, high resolution scanning electron mi- croscopy, high resolution transmission electron microscopy, diffuse reflectance spectroscopy and photoluminescence （PL） spectroscopy. The results indicated that the prepared photocatalysts showed high crystallinity with a uniform size distribution of the NPs. The degradation of cholorphenols is highly mandatory in today＇s scenario as they are affecting the environment adversely. Thus, the photocatalytic degradation of 4-chlorophenol （4-CP）, a potent endocrine disrupting chemical in aqueous medium was investigated by both pure and Mg-doped ZnO NPs under UV-light irradiation in the present study. The influence of the Mg content on the structure, morphology, PL character and photocatalytic activity of ZnO NPs were investigated systematically. Furthermore,the effect of different parameters such as 4-CP concentration, photocatalyst amount, pH and UV-light wavelength on the resulting photocatalytic activity was investigated.