稀土等碱性助剂对甲烷部分氧化制合成气整体式Ni/γ-Al2O3催化剂性能的影响

制备了整体式Ni/γ-Al2O3和添加稀土等碱性助剂的整体式Ni/γ-Al2O3催化剂. 研究了温度、烷氧比、空速和助剂等因素对甲烷部分氧化反应性能的影响,并利用XRD和TPR对催化剂进行了表征. 结果表明,催化剂活性随着温度的升高而增加;CH4转化率随着烷氧比的增加而降低;当空速为1×105 h-1时,整体式催化剂的催化性能最佳. 添加碱性助剂Ce,La,Na,Sr均有利于改善催化剂的还原性能,提高催化剂的活性. 其中添加稀土Ce,La可使副反应CH4+2 O2→CO2+2H2O 完全被抑制,从而使H2选择性达到100%.     

燃料对燃烧法制备Ni-Al_2O_3催化剂结构及浆态床甲烷化催化性能的影响

分别采用浸渍燃烧法和共燃烧法制备了一系列Ni-Al_2O_3催化剂,并对催化剂进行了表征,研究了燃料种类对不同方法制备的催化剂结构及浆态床CO甲烷化性能的影响.结果表明,以尿素、甘氨酸和乙二醇为燃料时,采用浸渍燃烧法制备的Ni-Al_2O_3催化剂织构性质均与载体相近,各催化剂金属Ni分散度和Ni晶粒相差不大,甲烷化性能接近,在260℃反应温度下CO转化率在80.1%~83.5%之间.而共燃烧法制备的Ni-Al_2O_3催化剂受燃烧过程影响明显,以甘氨酸和乙二醇为燃料时制得的催化剂比表面积较小,金属Ni分散度低且Ni晶粒较大,因而甲烷化活性较低;以尿素为燃料制备的催化剂比表面积大且Ni晶粒较小,CO转化率和CH_4选择性分别达到84.7%和91.1%.     

铈基复合氧化物催化碳烟燃烧的性能及其H2-TPR研究

采用溶胶-凝胶法或浸渍法制备了不同金属离子掺杂的铈基复合氧化物催化剂,并采用热重法考察其催化碳烟燃烧的活性,借助H₂-TPR(程序升温还原)手段探讨了催化剂氧化还原性对碳烟燃烧性能的影响. 结果表明,过渡金属的掺杂促使催化剂在低温下提供更多的表面氧和晶格氧,显著降低了碳烟的氧化温度,催化剂于200~400℃释放的活性氧数量对于碳烟燃烧性能提高至关重要; 而结构性助剂金属、碱金属或碱土金属的掺入可提高中温活性氧数量,虽然对碳烟起燃温度无明显改善,但加快了碳烟的燃烧速率.     

焙烧温度对柴油车氧化催化剂Pt-Pd-（x）ZrO2/Ce0.3Zr0.7O2-Al2O3性能的影响

制备了氧化铝、铈锆固溶体复合氧化物负载铂、钯的双金属催化剂Pt-Pd/ Ce0.3Zr0.7O2-Al2O3,并添加3% ZrO2助剂改性,用于柴油车尾气中CO、HC和NO的催化氧化,其中贵金属负载量仅为0.68 wt%。考察了制备过程中焙烧温度对催化剂性能的影响。催化剂活性评价结果表明,与未添加ZrO2的催化剂比较。添加ZrO2明显提高了催化剂的低温氧化活性,而且焙烧温度对催化剂的氧化性能有较大影响。焙烧温度为800 ?C时,CO和C3H6的起燃温度最低,分别为168、189 ?C,焙烧温度为700 ?C时,NO转化为NO2的转化率最高,最大转化率为36%,具有较好的热稳定性。通过XRD、N2吸附-脱附、CO化学吸附、XPS、H2-TPR等表征手段考察了催化剂物理化学性质随焙烧温度的变化情况,并分析了与催化剂活性之间的关系,得到贵金属分散度、表面化学吸附氧含量、催化剂的还原性质对氧化性能有重要影响,发挥协同作用。进而可以通过优化焙烧温度提升柴油车氧化催化剂性能,对提高工业应用柴油车尾气后处理系统的净化效率有重要意义。     

K/LiCoO2的制备及其同时催化去除碳烟和NOx的性能研究

采用溶液燃烧法和浸渍法制备了铜铁矿结构的钴酸锂(LiCoO2)及其负载K的系列催化剂样品,并通过XRD、NOx-TPD、H2-TPR、程序升温反应等对其进行了结构表征与性能评价.结果表明LiCoO2是一种能有效同时去除碳烟(PM)和NOx的催化剂;K负载可提高其催化活性,其中10%K/LiCoO2具有最低的PM起燃温度(246℃)和最大NOx→N2转化率(35.9%);催化剂表面生成的O2-/O-活性氧物种以及较强的NOx吸附存储能力可能是K/LiCoO2催化活性提高的原因.     

添加Cl离子对V_2O_5-WO_3/TiO_2催化剂低温NO转化率的影响

考察添加不同含量Cl离子对浸渍法制备的Cl-V_2O_5-WO_3/TiO_2催化剂低温NO转化率的影响。随着Cl离子质量添加量从0增加到2.5%,Cl-V_2O_5-WO_3/TiO_2催化剂NO转化率先升高后降低,结合在含有SO_2和H2O的SCR实验结果,确定1.5%Cl-V_2O_5-WO_3/TiO_2为性能最优催化剂。在反应温度为149-362℃,NO转化率大于95%;在145-385℃,NO转化率大于90%。采用XRF、BET、XRD、TG、FT-IR和H2-TPR等方法表征了催化剂的物理化学性能和结构。结果表明,在反应气氛中加入SO_2和H2O后,催化剂比表面积和孔容均减小,副反应产物含有NH+4和SO_2-4。适量Cl离子可以抑制硫物种沉积,减少副反应产物生成,增强催化剂抗中毒能力。     

Ce/Zr催化剂上碳颗粒物燃烧行为的研究

考察了CexZr1-xO2 (x=0,0.3,0.5,0.7,1.0)催化剂上碳颗粒物(碳颗粒物)的燃烧行为.结果表明: ZrO2对碳颗粒物燃烧无促进作用.含Ce催化剂能明显降低碳颗粒物的起燃温度.催化剂性能因Ce/Zr不同而不同.当Ce/Zr=5/5时,催化剂的活性最高.在催化剂中添加适量KNO3后,催化活性明显提高,碳颗粒物的起燃温度下降了140 ℃.     

金溶液pH值及浸泡处理对Au/Al2O3催化剂上CO氧化反应活性的影响

 采用阴离子浸渍法制备了Au/Al2O3催化剂,考察了溶液pH值及浸泡处理对催化剂上CO氧化反应的影响. 结果表明,催化剂的活性随着浸渍液氯金酸溶液pH值的升高而升高. 对于经300 ℃下H2还原处理的Au/Al2O3催化剂,无论用水浸泡还是用氨水浸泡,室温下CO转化率均可达到100%, 且催化剂具有良好的稳定性. 用氨水浸泡的催化剂经氧化处理后依然保持高活性,但用水浸泡的催化剂活性大幅度下降. XPS结果表明,用氨水浸泡的Au/Al2O3催化剂表面含有Al, O, C, N, Na和Au原子,但没有Cl原子存在. 这说明用氨水浸泡催化剂可有效除去Cl-离子而提高其催化活性.     

镍助剂对碳化钼催化剂的二苯并噻吩加氢脱硫性能的影响

 将MoO3和Ni-Mo混合氧化物在CH4/H2气氛中程序升温还原碳化制备了相应的碳化钼和碳化镍钼催化剂, X射线粉末衍射表征其物相分别为β-Mo2C和Ni-Mo2C. 考察了Ni助剂对碳化钼催化剂的制备及二苯并噻吩加氢脱硫反应性能的影响. 结果表明, Ni助剂的加入降低了碳化钼催化剂所需的还原碳化温度,提高了催化剂的比表面积,并对其二苯并噻吩加氢脱硫反应活性有明显的促进作用. Ni助剂添加量以Ni/Mo原子比为0.3为宜,此时Ni和Mo之间的催化协同效应达到最佳. 当反应压力为3.0 MPa, 反应温度为330 ℃, 空速8 h-1, H2/原料液体积比为500∶1时, 625 ℃还原碳化制备的碳化镍钼催化剂对0.6%二苯并噻吩/环己烷溶液的二苯并噻吩转化率达到96.25%, 较相应的碳化钼催化剂提高了1.57倍.     

堇青石负载La-Mn-O复合氧化物催化剂的甲苯催化燃烧性能

以堇青石蜂窝陶瓷为载体,以La2O3,Mn(NO3)2为基本原料,掺杂一些稀土等非贵重金属元素,采用浸渍法制备了系列负载La-Mn-O复合氧化物催化剂.考察了焙烧温度等对甲苯催化燃烧性能的影响,并对催化剂进行了XRD,TPR表征.结果表明,800 ℃焙烧的LaMn/Cord催化剂具有较高的甲苯催化燃烧性能;Ce取代催化剂中部分La后能改善催化剂的氧化活性,当Ce∶La=1∶1(摩尔比)时催化性能最佳,在260 ℃的反应温度下甲苯转化率达到90%以上.     

RDF pyrolysis by TG-FTIR and Py-GC/MS and combustion in a double furnaces reactor

With the increasing depletion of fossil energy, the refuse-derived fuel (RDF) as an unavoidable by-product of human activities has been used as an alternative fuel in the precalciner cement kilns. Since the RDF combustion also brings the problems of NOx pollution, it is quite important to find ways to lower the NOx emission during RDF combustion in the precalciner. The pyrolysis characteristics and products of RDF were studied by TG-FTIR and Py-GC/MS. From TG-FITR and Py-GC/MS tests, various carboxylic acids and alkenes formed with NOx released at the RDF pyrolysis process at 200–550 °C. By simulating the temperature (700 °C, 800 °C and 900 °C) and O₂ (12%, 14%, 16%, 18% and 21%) environment of the precalciner using a double furnaces reactor, the combustion processes and NOx formation characteristics of RDF combustion were studied. The results showed that the volatile-N was the dominant reactant source of fuel NOx during RDF combustion. The fuel-N conversion and NOx emission yield showed a continuous decreasing trend with temperature increasing from 700 to 900 °C. The fuel-N conversion and NOx emission yield showed a slight increasing trend with the oxygen concentration increase, and the optimum oxygen concentration for RDF combustion was 14%. In this study, the optimum temperature was 900 °C and oxygen concentration was 14% for de-NOx in the precalciner.

     

Ag/Co-Ce复合氧化物在O2及NOx气氛中催化燃烧碳烟的性能:Ag的作用

柴油车由于其良好的燃油经济性及强劲的动力得到了广泛应用,但同时柴油车尾气排放中颗粒物(PM)也对环境造成巨大污染,并严重威胁人类健康.与气体污染物相比,PM的处理难度更大,其组分复杂,起燃温度高,是当前柴油车排放问题的瓶颈和难点.颗粒过滤器(DPF)是一种有效消除PM的手段,它需要及时再生以保证其较高的碳烟捕集效率.与其他再生方案相比,连续催化再生系统工艺简单,能耗低,研发一种能够连续催化再生柴油车DPF的催化剂也成为当务之急.Ag是一种比较特殊的贵金属,其工业属性较强,价格也相对低廉.Ag基催化剂在环境催化领域有着广泛应用,已被应用于CO催化氧化、VOC催化去除及甲醛催化氧化等领域.目前的文献报道主要集中于研究Ag基催化剂负载于惰性载体对O2气氛下碳烟起燃性能的影响,并基于此讨论Ag的作用.本文利用柠檬酸络合法合成了高性能低温催化氧化材料体系xAg/Co0.93Ce0.07,探讨了不同Ag负载量对在两种气氛O2及O2+NO中催化性能的影响,并深入分析了引起此现象的原因.结果表明,Ag对Co-Ce复合氧化物的催化性能有显著的促进作用;Ag/Co-Ce复合氧化物在O2气氛下的起燃活性取决于Ag含量,Ag含量最高的样品0.3Ag/Co0.93Ce0.07催化性能最佳.而在NOx气氛下,Ag基催化剂的起燃性能不及在O2中的数值;0.2Ag/Co0.93Ce0.07与0.3Ag/Co0.93Ce0.07催化活性并列最优,其起燃温度可低至226oC.XRD及Raman的表征结果证实了Ag主要以单质形态存在,且其对Co-Ce复合氧化物的晶体结构未产生显著的影响,Ag的晶粒尺寸也未明显变化.H2-TPR则表明了Ag的负载未能提高催化剂的整体氧化还原能力,soot-TPR预示Ag甚至恶化了催化剂在惰性气氛下表面晶格氧及体相晶格氧的活性.NOx-TPD表征结果则证明了Ag对催化剂的NOx吸附有积极作用.此外,Ag/Co-Ce复合氧化物催化剂也具备了优异的耐久性及稳定性.本文还依据催化性能及表征结果剖析了碳烟在不同气氛下的催化氧化机理.在O2气氛下,Ag为反应的活性位,Ag与其表面的氧化物层AgOy之间存在一个自再生的反应循环.Ag吸附解离氧原子后,将其转化为AgOy,这表明此氧化物层不仅能够在低温下贡献表面晶格氧去除碳烟,促进氧分子向超氧物种转化,它在分解后也能将吸附氧解离为过氧物种及超氧物种.在NOx气氛下,催化剂表面硝酸根物种是催化剂催化性能维持稳定的重要因素;反应过程中催化材料表面硝酸盐物种的热稳定性筛查结果也进一步佐证了催化剂表面的AgNO3物种是碳烟起燃的决定性因素,其自身的氧化还原活性及Ag离子移动性均有利于降低碳烟的起燃温度.TGA结果说明了NOx气氛中的活性中间产物AgNO3的氧化还原活性劣于O2气氛下活性中间产物Ag2O,这直接导致催化剂在O2气氛下具备更好的碳烟起燃性能.本文工作有助于启发其他研究者开发高活性催化氧化催化材料.     

ZrxTixAl1-2xO2的制备及其在三效催化剂上的应用

Zr_0.5Ti_0.5O₂(ZT) and Zr_0.25Ti_0.25Al_0.5O₂(ZTA) mixed oxides were prepared by co-precipitation method and characterized by low temperature adsorption-desorption， XRD and NH₃-TPD. The activity of Pt/Zr_0.5Ti_0.5O₂ and Pt/ Zr_0.5Ti_0.5Al_0.5O₂ catalysts was evaluated using the simulated gases. The results show that ZTA samples exhibit higher specific surface area， larger pore volume and proper surface acidic amount and acidity in comparison with ZT. The results of the catalytic test indicate that Pt/ZT and Pt/ZTA catalysts exhibit excellent low-temperature catalytic activity and lower light-off temperatures of hydrocarbon， carbon monoxide and nitrogen oxides， especially better conversion for nitrogen oxides (NO_x). The addition of Al₂O₃ into ZT enhanced the anti-aging property of Pt/ ZTA catalysts due to the excellent textural， structural， surface acidity and thermal stability.     

Pd catalysts supported on modified Zr0.5Al0.5O1.75 used for lean-burn natural gas vehicles exhaust purification

Composite supports Zr0.5Al0.5O1.75 modified by metal oxides,such as La2O3,ZnO,Y2O3 or BaO,were prepared by co-precipitation method,and palladium catalysts supported on the modified composite supports were prepared by impregnation method.Their properties were characterized by X-ray diffraction(XRD),NH3 temperature-programmed desorption(NH3-TPD),H2 temperature-programmed reduction(H2-TPR),N2 adsorption/desorption,and CO-chemisorption.The catalytic activity and the resistance to water poisoning of the prepared Pd catalysts were tested in a simulated exhaust gas from lean-burn natural gas vehicles with and without water vapor.The results demonstrated that the modified supports had an apparent effect on the performance of Pd catalysts,compared with the Pd catalyst supported on the unmodified ZrAl.The addition of ZnO or Y2O3 promoted the conversion of CH4.In the absence of water vapor,Pd/ZnZrAl exhibited the best activity for CH4 conversion with the light-off temperature(T50) of 275℃ and the complete conversion temperature(T90) of 314℃,respectively.However,in the presence of water vapor,Pd/YZrAl was the best one over which the light-off temperature(T50) of methane was 339℃ and the complete conversion temperature(T90) was 371℃.These results indicated that Pd catalyst supported on the modified composite ZrAl support showed excellent catalytic activity at low temperature and high resistance to H2O poisoning for the exhaust purification of lean-burn natural gas vehicles.     

High surface area MoO3/TiO2 hydrodesulfurization catalysts

The catalytic combustion of benzene over SBA-15-supported copper oxide has been investigated. The SBA-15-supported copper oxide catalysts have been prepared by the precipitation-deposition method, and characterized by XRD, BET and TPR. In the CuO/SBA-15 catalysts, the catalytic activity increases with increasing copper oxide loading ratio. Metallic Cu is much more active than copper oxides. When the reduction temperature increases to 500°C the benzene conversion increases until the maximum vlaue is obtained. Further increase in the reduction temperature to 600°C results in a decrease of benzene conversion.     

Ce-Zr-La-Al2O3的制备及负载的单Pd三效催化剂

采用共沉淀和浸渍两种方法制备了Ce-Zr-La-Al2O3(CZLA),对其进行了N2吸附和X射线衍射分析.以CZLA为载体制备了2%Pd/CZLA三效催化剂,并对催化剂进行了程序升温还原和活性测试.结果表明,两种方法制备的CZLA均具有较好的结构、织构和储氧性能,共沉淀法制备的CZLA具有更好的抗老化性能.以CZLA为载体所制备的单Pd三效催化剂表现出低的起燃温度、优异的三效性能,特别是优异的转化NO性能及抗老化性能.     

载体硫酸化对柴油机尾气催化剂Pt/Ce-Zr活性和稳定性的影响

近年来,随着大气环境污染问题日益严重,汽车尾气排放受到政府越来越严苛的控制.柴油车排气成分主要包括碳氢化合物(HC)、一氧化碳(CO)、氮氧化物(NOx)、微粒(PM)和二氧化硫(SO2),因此常用的尾气后处理系统有颗粒捕获器(DPF)、氧化型催化转换器(DOC)以及NOx选择还原系统(SCR),在处理尾气时三者联合使用.其中柴油机氧化型催化剂(DOC)是汽车尾气后处理装置的重要组成部分,主要用于氧化CO,HC和NO,可以将CO和HC氧化成无害的CO2和H2O,将NO氧化成NO2,为后续SCR反应提供条件.柴油机排气温度一般较低(150?400°C),特别是在冷启动阶段,排气温度可降低到100°C左右,要求催化剂具有良好的低温催化活性.此外,由于柴油中存在少量含硫有机化合物,经过燃烧分解,使得柴油机尾气中含有少量SO2,对催化剂又有钝化作用,因此催化剂的抗硫性也是需要关注的重点.本文采用浸渍法制备Pt/Ce-Zr-SO42?催化剂,考察了催化剂载体硫酸化以及Pt和H2SO4的负载顺序对催化剂催化氧化C3H6和CO的活性及抗硫性的影响,并且对Pt/Ce-Zr-SO42?催化剂进行了一系列表征,探究其物理化学性质.结果表明,SO42?的添加能有效提高催化剂活性.Pt/CZ-10S对C3H6和CO的T90(转化率为90%时的温度)相较于Pt/CZ催化剂降低了约75°C,另外,Pt/CZ-10S催化剂也表现出较好的抗硫稳定性,在含硫尾气中240°C反应20 h后,其对C3H6和CO的转化率仍保持在95%以上.CO-TPD和XPS分析结果显示,Ce-Zr-SO42?载体上Pt的分散度增加,增加的Pt颗粒可以产生更多新的活性位点(Pt&+-(SO42?)&?couples),从而表现出优异的催化活性.此外,硫酸化后催化剂表面酸性的变化也是其抗硫性能提高的原因.     

介质阻挡放电等离子体与吸附在CuZSM-5上的NO或NO/O2的相互作用

采用吸附和程序升温脱附(TPD)技术研究了介质阻挡放电等离子体对CuZSM-5催化剂上吸附的氮氧化物作用. 实验表明, 介质阻挡放电等离子体使催化剂表面吸附的NO及Cu活性位上吸附的NOx物种脱附, 并引发表面化学反应生成新的氮氧化物. 对于NO/N2体系, 介质阻挡放电等离子体与吸附在CuZSM-5上NO作用, 主要生成N2O和O2. 在富氧体系NO/O2/N2, 则生成较大量的N2O、NO2和NO. 等离子体预处理活性下降的CuZSM-5, 可明显提高其催化分解NO活性. 对比有或无介质阻挡放电等离子体预处理NO或NO/O2饱和吸附的CuZSM-5上的NO-TPD结果表明, 等离子体提高催化剂活性的原因与其使催化剂Cu活性位上吸附的NOx物种脱附有关.     

Study on the combustion kinetic characteristics of biomass tar under catalysts

TG and DTA experiments were performed to investigate the biomass tar combustion behavior in coexistence of dolomite and mayenite at two different heating rates as 5 and 15°C min⁻¹. Different reaction kinetic mechanisms with the classical Arrhenius model were used to treat TG data, and showed that the first-order combustion model fitted the data well. Three stages combustion model was proposed and applied for the calculation of kinetics parameters successfully. The starting temperature of high temperature combustion stage moved up near 100°C because of the coexistence catalysts, and the combustion amount of biomass of the stage also improved nearly 10 mass%. By calculation a uniform trend of decreasing activation energies was observed with the addition of dolomite and mayenite, and also greatly improved the amount and speed of tar combustion process.