Al2O3为载体的催化剂净化贫燃汽车尾气研究

在富氧条件下,考察了C₃H₆和C₂H₅OH在Ag/Al₂O₃、In/Al₂O₃、Sn/Al₂O₃、Co/Al₂O₃、Pt/Al₂O₃和Ag/Al₂O₃+Pt/Al₂O₃组合催化剂上选择性还原NO的性能.结果表明,Ag/Al₂O₃具有最高的NO还原活性.在负载型过渡金属氧化物催化剂上,会生成显著量的CO,其HC和CO氧化转化温度也远远高于Pt/Al₂O₃催化剂.串联组合Ag/Al₂O₃+Pt/Al₂O₃催化剂可显著拓宽活性温度范围,促进HC和CO氧化,降低N₂O和CH₃CHO生成量.     

N2O decomposition over K/Na-promoted Mg/Zn-Ce-cobalt mixed oxides catalysts

Three groups of cobalt mixed oxide catalysts（Mg/Zn-Co, Mg/Zn-Ce-C, K/Na-Mg/Zn-Ce-Co）were prepared by sol-gel or impregnation methods. The synergistic effects of transition metal, rare earth metal and alkali metal on cobalt mixed catalysts for nitrous oxide（N2O）decomposing to N2 and O2were investigated. The experimental results revealed that the catalytic activity for N2 O decomposition was promoted as Co2＋was replaced partially by Zn2＋/Mg2＋, moreover, the characterization analysis by XRD and XPS showed that Zn2＋/Mg2＋replaced Co2＋successfully into the spinel structure of Co3O4 and promoted significantly the catalytic activity. Especially, the addition of CeO2 and K2O/Na2O decreased the binding energy and resulted in an increase in the density of the electron cloud around Co and an improvement of the catalytic activity. Of the investigated cobalt mixed catalysts, the best catalytic activity was shown by 2% K-Zn0.5-Ce0.05-Co catalyst.     

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.     

Toluene decomposition performance and NOx by-product formation during a DBD-catalyst process

Characteristics of toluene decomposition and formation of nitrogen oxide(NOx) by-products were investigated in a dielectric barrier discharge(DBD) reactor with/without catalyst at room temperature and atmospheric pressure. Four kinds of metal oxides, i.e., manganese oxide(Mn Ox), iron oxide(Fe Ox), cobalt oxide(Co Ox) and copper oxide(Cu O), supported on Al2O3/nickel foam, were used as catalysts. It was found that introducing catalysts could improve toluene removal efficiency, promote decomposition of by-product ozone and enhance CO2 selectivity. In addition, NOx was suppressed with the decrease of specific energy density(SED) and the increase of humidity, gas flow rate and toluene concentration, or catalyst introduction. Among the four kinds of catalysts, the Cu O catalyst showed the best performance in NOx suppression. The Mn Ox catalyst exhibited the lowest concentration of O3 and highest CO2 selectivity but the highest concentration of NOx. A possible pathway for NOx production in DBD was discussed. The contributions of oxygen active species and hydroxyl radicals are dominant in NOx suppression.     

Performance and mechanism study for low-temperature SCR of NO with propylene in excess oxygen over Pt/TiO2 catalyst

A 0.5 wt.% Pt/TiO2 catalyst was prepared and used for the low-temperature selective catalytic reduction(SCR) of NO with C3 H6 in the presence of excess oxygen.The effects of Pt loading and O2 concentration on Pt/TiO2 catalytic performance for low-temperature SCR were investigated.It was found that optimal Pt loading was 0.5 wt.% and excess O2 favored low-temperature SCR of NOx.The mechanism of low-temperature SCR of NO with C3 H6 was investigated with respect to the behavior of adsorbed species over Pt/TiO2 at 150°C using in situ DRIFTS.The results indicated that surface nitrosyl species(Pt δ+-NO and Ti 3+-NO) and Pt 2+-CO are main reaction intermediates during the interactions of NO,C3 H6 and O2.A simplified NO decomposition mechanism for the low-temperature SCR of NO with C3 H6 was proposed.     

超声波浸渍法制备V_2O_5-WO_3/TiO_2选择性催化还原脱硝催化剂

采用超声波浸渍法、传统浸渍法制备一系列V2O5-WO3/TiO2催化剂,对催化剂的反应活性进行考察。研究表明:与普通浸渍法相比,超声波浸渍法可以提高催化剂的脱硝效率,拓宽催化反应的温度窗口。超声波浸渍时间和超声波功率对催化剂的反应活性有较大影响。浸渍时间增加,催化剂脱硝效率也随之提高。超声波功率增加,催化剂的脱硝效率先提高后降低。在超声波频率28 kHz,超声波功率400 W,超声作用时间1.5 h,超声水粉比为100 mL H2O/10 g TiO2的条件下,制得的V2O5-WO3/TiO2脱硝催化剂脱硝效率接近100%。通过SEM对制备的催化剂进行表征,超声波浸渍法制备的催化剂的活性成分在载体上分散更加均匀。     

氮掺杂二氧化钛负载钒磷氧催化氧化NO的实验研究

以VPO为活性组分,N掺杂TiO 2为载体,采用浸渍法制备了VPO/TiN催化剂,基于单因素实验研究了其对NO的选择性催化氧化(SCO)性能以及抗硫抗水性能。研究表明:当P/V为1/5、N/Ti为1、活性组分负载量为10%、焙烧温度为350℃时,催化剂的SCO活性最好,NO氧化率达到61%;光致发光光谱(PL)表征显示N掺杂TiO 2在催化剂表面形成的氧空位可增强催化剂对O 2的吸附;VPO/TiN催化剂抗硫抗水性能较强,反应后的催化剂表面未发现硫酸根的特征峰,水蒸气主要通过与NO竞争吸附占据活性位点来抑制催化剂的SCO活性。     

Mn-Ce-Co/TiO2催化剂低温脱硝活性研究

以纳米TiO2为载体,通过浸渍法制备一系列改性Mn-Ce/TiO2脱硝催化剂.通过实验考察不同元素组分催化剂的脱硝活性,同时探讨金属氧化物掺杂对提高催化剂低温脱硝活性的机理.活性测试结果显示,Co掺杂能最有效地提高Mn-Ce/TiO2催化剂在低温段的SCR脱硝活性,在n(Co):n(TiO2)=0.08～0.10、体积空速为35100h-1的条件下,催化剂在120℃时就能达到80%以上的NO去除率,140℃左右时的NO去除率接近100%.BET、XRD、TPR、TPD等表征测试结果表明,Co掺杂可改进Mn-Ce/TiO2催化剂的物化特性,增加催化剂表面的活性酸位点及活性氧数量,提高催化剂的氧化还原能力,从而提高Mn-Ce/TiO2催化剂低温SCR脱硝活性.     

不同方法制备的铟催化剂选择性还原NO

不同负载量的In/Al₂O₃催化剂分别以浸渍法、共沉淀法和溶胶-凝胶法制得,对比评价了不同方法制备的样品在富氧条件下以丙烯为还原剂,选择性催化还原NO的活性,考察了氧气浓度、H₂O对活性的影响.研究表明,铟催化剂有较高的去除NO活性,制备方法对催化剂活性具有显著影响.其中,溶胶-凝胶法和共沉淀法最高活性都可达90%左右;而浸渍法样品的活性较差,最高转化率不到60%.氧气浓度对NOx最高转化率及其相应反应温度均有重要影响.随着O2浓度的提高,最高活性对应的反应温度降低.反应气氛中H₂O的加入使铟催化剂活性大幅降低.铟与其他多种金属活性组分相比,一个突出的不同表现是,3种方法各自的最佳负载量相差不大.     

Decomposition of hexachlorobenzene over Al2O3 supported metal oxide catalysts

Decomposition of hexachlorobenzene(HCB)was investigated over several metal oxides(i.e.,MgO,CaO,BaO,La2O3,CeO2,MnO2, Fe2O3,and Co3O4)supported on Al2O3,which was achieved in closed system at a temperature of 300°C.Catalysts were prepared by incipient wetness impregnation with different metal oxides loading and impregnating solvents.The decomposition effciency of different catalysts for this reaction depends on the nature of the metal oxide used,and Al2O3 supported La2O3 was found to be the most active one.Pe...     

不同硅铝比Fe-ZSM-5催化剂对氧化亚氮催化分解性能的研究

以不同硅铝比的H-ZSM-5分子筛为载体,采用离子交换法和化学气相沉积法制备Fe-ZSM-5催化剂,并用XRD、BET、TEM、UV-vis和NH3-TPD等表征手段对催化剂进行分析,研究催化剂中铁的存在状态.结果表明,分子筛的硅铝比影响铁在分子筛中的分布形态,化学气相沉积法和热离子交换法制得硅铝比为25的Fe-ZSM-5-25分子筛催化剂上均匀地分布着粒径为8 nm左右的纳米氧化铁颗粒,并且Fe-ZSM-5-25分子筛催化剂比Fe-ZSM-5-300更容易形成Fe3+x O y团簇.制得的Fe-ZSM-5分子筛催化剂催化分解氧化亚氮(N2O),结果表明,相同的制备方法,硅铝比小的Fe-ZSM-5-25催化剂对N2O分解活性更好;相同硅铝比的Fe-ZSM-5催化剂,采用化学气相沉积法制得的对N2O分解活性最好.另外,O2的存在对Fe-ZSM-5上N2O催化分解活性有抑制作用,而NO对N2O催化分解活性展示了一定的正效应.最后,经过100 h的连续反应,Fe-ZSM-5催化剂依然能够保持催化活性.     

Effects of synthesis methods on catalytic activities of CoOx–TiO2 for low-temperature NH3-SCR of NO

A series of cobalt doped TiO_2(Co-TiO_2) and Co Oxloaded TiO_2(Co/TiO_2) catalysts prepared by sol–gel and impregnation methods respectively were investigated on selective catalytic reduction with NH_3(NH_3-SCR) of NO. It was found that Co-TiO_2 catalyst showed more preferable catalytic activity at low temperature range. From characterization results of XRD,TEM, Raman and FT-IR, Co species were proved to be doped into TiO_2 lattice by replaced Ti atoms. After being characterized and analyzed by NH_3-TPD, PL, XPS, EPR and DRIFTS, it was found that the better NH_3-SCR activities of Co-TiO_2 catalysts, compared with Co/TiO_2 catalyst, were ascribed to the formation of more oxygen vacancies which further promoted the production of more superoxide ions(O-2). The superoxide ions were crucial for the formation of low temperature SCR reaction intermediates(NO-3) by reacting with adsorbed NO molecule. Therefore, these aspects were responsible for the higher low temperature NH_3-SCR activity of Co-TiO_2 catalysts.     

Unraveling SO2-tolerant mechanism over Fe2（SO4）3/TiO2 catalysts for NOx reduction

Developing low-temperature SO₂-tolerant catalysts for the selective catalytic reduction of NO_x is still a challenging task. The sulfation of active metal oxides and deposition of ammonium bisulfate deactivate catalysts, due to the difficult decomposition of the as-formed sulfate species at low temperatures（<300 °C）. In recent years, metal sulfate catalysts have attracted increasing attention owing to their good catalytic activity and strong SO₂ tolerance at hi...     

长江中下游河流沉积物和悬浮物中金属元素的形态特征

采集长江中下游8个样点沉积物和悬浮物样品,用连续提取方法提取金属元素的5种化学形态（可交换态、碳酸盐结合态、铁锰氧化物结合态、有机质－硫化物结合态和残渣态）,用等离子体发射光谱（ICP－AES）分析所有样品中锂、钠、钾、镁、钙、锶、钛、钒、铬、锰、钴、镍、铝、钇和锆共15种元素各化学形态的含量,并用聚类分析方法研究这些元素在形态上的分类特点。结果表明：在沉积物和县浮物中,碱金属元素（锂、钠、钾）主要以残渣态和可交换态存在;碱土金属元素（镁、钙、锶）各形态含量较为均匀,但钙的碳酸盐态含量很高;锰和钴的铁锰氧化物态含量较高;铁族元素除锰和钴以外（钛、钒、铬、镍）、铝和锆残渣态含量高、其它形态含量低。所研究元素中,钙和锰的残渣态含量最低。     

高湿度条件下分解臭氧的锰催化剂

分别以硝酸锰和乙酸锰为前体 ,用浸渍法制备了MnOx γ Al2 O3催化剂 ,考察了它们对高湿度高浓度臭氧的催化分解性能。分析了在不同的温度煅烧和用不同的前体制备的催化剂上的氧化锰的形态。实验表明 ,以乙酸锰为前体 ,在 4 0 0℃煅烧得到的催化剂的臭氧催化分解活性最高 ,保持 95 %的臭氧分解率 ,其使用寿命在 10 0h以上 ,该催化剂上锰的主要形态为Mn2 O3,在载体上分散性最好     

Catalytic reduction of nitric oxide with carbon monoxide on copper-cobalt oxides supported on nano-titanium dioxide

A series of copper-cobalt oxides supported on nano-titanium dioxide were prepared for the reduction of nitric oxide with carbon monoxide and characterized using techniques such as XRD, BET and TPR. Catalyst CuCoOx/TiO2 with Cu/Co molar ratio of 1/2, Cu- Co total loading of 30% at the calcination temperature of 350°C formed CuCo2O4 spinel and had the highest activity. NO conversion reached 98.9% at 200°C. Mechanism of the reduction was also investigated, N2O was mainly yielded below 100°C, while N2 was produced instead at higher temperature. O2 was supposed to accelerate the reaction between NOx and CO for its oxidation of NO to give more easily reduced NO2, but the oxidation of CO by O2 to CO2 decreased the speed of the reaction greatly. Either SO2 or H2O had no adverse impact on the activity of NO reduction; however, in the presence of both SO2 and H2O, the catalyst deactivated quickly.     

富氧条件下Ag、Co和Cu/Al2O3选择性催化还原NO的研究

研究了负载于氧化铝载体上的Ag、Co和Cu 3种金属催化剂在富氧条件下以丙烯为还原剂,选择性催化还原NO的活性,考察了这3种金属单独负载时其负载量与活性的关系,并尝试探讨了这几种金属活性组分之间的一些组合效应.研究表明,单组分催化剂以Ag的活性最佳,达近90%,Co其次,Cu最低.相应的最佳活性温度则是Cu最低,Ag最高.对于单组分Ag催化剂,相同负载量的分步浸渍与一步浸渍样品活性无明显差异.机械混合样品的活性不是单组分样品活性的简单加和.其中,以Ag-Co机械混合样品的活性最佳,最高活性高于80%.复合催化剂一步浸渍与分步浸渍样品的活性均有不同程度的下降,一步浸渍的几个样品的活性下降尤为明显,最高活性只有30%多.     

青岛近海不同天气状况下大气气溶胶中金属元素浓度分布特征研究

为探究青岛近海不同天气下气溶胶中金属元素的浓度分布特征,于2012年4~5月,2012年8月~2013年3月在青岛近海采集了总悬浮颗粒物(TSP)样品,利用电感耦合等离子体质谱法(ICP-MS)和电感耦合等离子体原子发射光谱法(ICPAES)分析了主要微量金属元素.结果表明,Al、Ca、Fe、Na、K和Mg是TSP中主要的金属元素,质量浓度占所测元素总浓度的94.2%.TSP及金属元素浓度月变化明显,Fe、Al、K、Ca、Mg、Zn、Ba、Mn、Ti、Sr和Li均在11月和1月浓度最高,Be、Sc、Co、Ni和Cr在1月最高,Na在8、11和2月较高,12月最低,Pb在1月和2月最高,8月和12月最低.富集因子表明Be、Co、Al、Ca、Fe、K、Mg、Mn、Sr和Ti主要受自然源影响,Li、Cr、Ni、Zn、Ba和Na除受自然源外,还受部分人为源影响,Pb主要来自人为源.不同天气状况对TSP及其金属元素浓度影响较大,除Ti外,所测元素浓度均在烟雾天最高.与晴天相比,烟雾天除Ti外,其余元素均升高,增幅为1~4倍,雾天Li、Be、Cr、Ni、Al、Fe、Mg和Mn变化不大,Pb和Na升高较多,Co、Ca和Ti降低较多,霾天Cr、Co和Ti降低,其余元素浓度升高,增幅为1~3倍.大部分元素在晴天富集因子最小,雾天富集因子最大.Ni、Zn、Ba、K、Na、Pb和Sr富集因子为晴<霾<烟雾<雾,Fe和Mn为晴<烟雾<霾<雾,Al和Mg为晴<雾<霾<烟雾,其余金属不同天气下富集因子的变化规律各不相同.     

铈钴复合氧化物催化剂催化CO-SCR反应机理研究

利用共沉淀法制备了一系列Ce-Co-O_x复合氧化物催化剂,并对其CO-SCR反应性能进行了研究.考察了Co和Ce比例对CO-SCR反应活性的影响,确定最佳的Ce和Co复合比例为3：7,最高转化率为84%（250℃）.经表征分析发现,Ce（0.3）-Co（0.7）-O_x上发生CO-SCR的主活性位点是Co.掺杂Ce提升催化性能主要有两方面原因：一是催化剂比表面积增大,提高了表面的吸附位数量;二是Ce-Co-O_x催化剂形成的固溶体提升了氧迁移率.反应机理可能是气态或者弱吸附状态的CO与NO的吸附物种（主要是桥接二齿亚硝酸盐物种和螯合式双齿硝酸盐物种）反应.     

A comparative investigation of NdSrCu_(1-x)Co_xO_(4-δ) and Sm_(1.8)Ce_(0.2)CU_(1-x)Co_xO_(4-δ) (x: 0-0.4) for NO decomposition

A series of single-phase T-structured NdSrCu_(1-x)Co_xO_(4-δ) with oxygen vacancies and T'-structured Sm_(1.8)Ce_(0.2)Cu_(1-x)Co_xO_(4-δ) (x:0-0.4) with oxygen excess were prepared using ultrasound-assisted citric acid complexing method, and characterized by means of techniques such as thermogravimetric analysis and NO temperature-progranuned desorption (NO-TPD). The catalytic activities of these materials were evaluated for the decomposition of NO. It was found that the NdSrCut_xCoxO4_b catalysts were of oxygen vacancies whereas the Sm_(1.8)Ce_(0.2)CU_(1-x)Co_xO_(4-δ) ones possessed excessive oxygen (i.e., over-stoichiometric oxygen); with a rise in Co doping level,the oxygen vacancy density of NdSrCu_(1-x)Co_xO_(4-δ) decreased while the over-stoichiometric oxygen amount of Sm_(1.8)Ce_(0.2)CU_(1-x)Co_xO_(4-δ)increased. The NO-TPD results revealed that NO could be activated much easier over the oxygen-deficient perovskite-like oxides than over the oxygen-excessive perovskite-like oxides, with the NdSrCuO_(3.702) catalyst showing the best efficiency in activating NO molecules. Under the conditions of 1.0% NO/helium, 2800 hr~(-1), and 600-900℃, the catalytic activity of NO decomposition followed the order of NdSrCuO_(3.702)> NdSrCu_(0.8)Co_(0.2)O_(3.736) > NdSrCu_(0.6)Co_(0.4)O_(3.789) > Sm_(1.8)Ce_(0.2)Cu_(0.6)Co_(0.4)O_(4.187)> Sm_(1.8)Ce_(0.2)Cu_(0.8)Co_(0.2)O_(4.104)> Sm_(1.8)Ce_(0.2)CuO_(4.045), in concord with the sequence of decreasing oxygen vacancy or oxygen excess density. Based on the results, we concluded that the higher oxygen vacancy density and the stronger Cu~(3+)/Cu~(2+) redox ability of NdSrCu_(1-x)Co_xO_(4-δ) account for the easier activation of NO and consequently improve the catalytic activity of NO decomposition over the catalysts.