Pd/ZrO【sub】2【/sub】-Al【sub】2【/sub】O【sub】3【/sub】催化剂加氢脱硫性能的研究

采用等体积浸渍法制备了一系列不同Zr含量的ZrO2-Al2O3复合载体和Pd/ZrO2-Al2O3催化剂,利用连续流动微反装置考察了Pd/ZrO2-Al2O3催化剂的噻吩加氢脱硫(HDS)性能,并运用程序升温还原(TPR),程序升温脱附(H2-TPD,NH3-TPD)和N2物理吸附等技术对载体及催化剂进行了表征.结果表明:ZrO2-Al2O3复合载体中Zr含量对Pd基催化剂的HDS性能有较大影响,加入适量Zr可增大Pd/Al2O3催化剂的分散度及H2吸附量和酸量,减弱活性组分与载体的相互作用,使活性中心和噻吩吸附位增多以及活化能降低,从而有利于Pd基催化剂HDS反应活性的提高,w(Zr)为9%时Pd/ZrO2-Al2O3催化剂的活性最好.     

催化剂Ru/ZrO2-CeO2催化湿式氧化苯酚

催化剂Ru/ZrO2-CeO2催化湿式氧化苯酚的过程表明,Ru/ZrO2-CeO2可以显著提高COD和苯酚去除效果,当反应温度为170℃,压力为3 MPa,反应120 min后,COD和苯酚的去除率分别达到了99%和100%.试验还考察了不同反应条件对苯酚溶液COD去除的影响,并获得了最优的反应条件:温度为170℃,压力为3 MPa,催化剂的投加量为5 g/L,搅拌速度为500 r/min.通过对中间产物的分析,本研究提出了催化湿式氧化苯酚的简单路径图,认为苯酚首先被氧化成小分子有机酸,接着小分子有机酸被氧化成二氧化碳和水.前一个过程是快速反应,后一个过程中的乙酸氧化是慢速过程,需要在高温下才能完成.乙酸的氧化主要是自由基攻击α碳上的C-H键,先生成甲酸,并最终生成二氧化碳和水.     

ZrO2掺杂对La2Ce2O7力学和热物理性能 影响的研究

目的提高La_2Ce_2O_7(LC)陶瓷材料的断裂韧性。方法采用固相反应方法合成Y_2O_3稳定ZrO_2(YSZ)掺杂的La_2Ce_2O_7(LC)陶瓷材料(LCZ),研究LCZ块材的弹性模量、断裂韧性等力学性能,以及热膨胀系数、热传导率等热物理性能。结果 10%YSZ摩尔分数掺杂的LCZ块材的断裂韧性约为1.4 MPa·m1/2,比LC提高了近10%。YSZ掺杂有效地抑制了LC在200～400℃温度区间热膨胀系数下降的现象。在200～1200℃温度范围内,LCZ块材的热膨胀系数为10×10-6～12×10-6K-1,在1200℃的热导率约为0.75W/(m·K),比YSZ降低了50%以上,显示了优异的隔热性能。结论 YSZ的掺杂使LC中部分Zr4+取代了La3+,降低了晶格中的O空位浓度,原子的横向剪切运动被削弱,有效地抑制了LC在200～400℃温度区间热膨胀系数下降的现象。由于t-ZrO_2→m-ZrO_2的相变对微裂纹的愈合作用,10%YSZ掺杂使LC块材的断裂韧性得到有效提高。     

ZrO2掺杂对V2O5-MoO3/TiO2催化剂脱硝性能的影响

采用浸渍法制备了一系列V₂O₅-MoO₃/TiO₂和V₂O₅-MoO₃/TiO₂-ZrO₂催化剂,考察了ω(V₂O₅/TiO₂)、ω(MoO₃/TiO₂)及ω(ZrO₂/TiO₂)对催化剂选择性催化还原NO性能的影响。结果表明:ω(V₂O₅/TiO₂)为3%,ω(MoO₃/TiO₂)为6%,ω(ZrO₂/TiO₂)为30%的催化剂具有最佳的脱硝活性、较低的SO₂氧化率及较好的抗硫抗水性能。采用XRD、TG、BET、SEM、H₂-TPR及NH₃-TPD等手段,对上述催化剂的理化性能及结构进行表征。结果表明:掺杂ZrO₂的催化剂具有更好的选择性催化还原NO活性,这与其较大的比表面积、较多的表面羟基、均匀的粒径、优良的氧化还原性能和较多的弱酸性位有关。     

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.     

颗粒Ru催化剂催化湿式氧化乙酸和苯酚

采用湿式成型法制备了Ru/ZrO₂-CeO₂颗粒催化剂,对乙酸和苯酚进行湿式氧化,研究反应条件对苯酚氧化过程中COD去除的影响,并对催化剂的稳定性进行评价.结果表明,向CeO₂中添加Zr能提高催化剂抗热性能,使用湿式成型法能降低焙烧温度,两者都可以提高比表面积和催化剂活性.Ru/ZrO₂-CeO₂催化湿式氧化苯酚的COD去除率随着反应温度的升高、压力的增大和催化剂使用量的增加而升高,最优反应条件为温度150℃,压力3MPa,催化剂用量35g/L.在110h的动态试验中,COD和苯酚的去除率高于90%,催化剂具有较高活性和良好的稳定性.     

A simple and cheap method for preparation of coupled ZrO2/ZnO with high photocatalytic activities

The objective of this study was to prepare a new photocatalyst with high activities for degradation of organic pollutants. Coupled ZrO₂/ZnO photocatalyst was prepared with a simple precipitation method with cheap raw materials zinc acetate and zirconium oxychloride, and was characterized by X-ray diffraction (XRD) and transmission electron microscopy (TEM). Reactive brilliant red X-3B was used as a model compound to investigate the photocatalytic activity of synthesized catalysts in water under 254 nm UV irradiation. Results show that the optimal calcination temperature and coupling molar ratio of Zr were 350°C And 2.5%, respectively. At the calcination temperature of 350°C, ZrO₂ was dispersed on the surface of hexagonal ZnO in the form of amorphous clusters. The particle size of ZrO₂/ZnO decreased with the decrease of calcination temperature and the increase of Zr coupling amount. ZrO₂/ZnO has better photocatalytic activity for degradation of reactive brilliant red (RBR) X-3B than pure ZnO and P25-TiO₂.     

焙烧温度对CeO_2(ZrO_2)/TiO_2选择性催化脱硝性能的影响

采用溶胶-凝胶法并以不同温度焙烧制备一系列CeO_2(ZrO_2)/TiO_2(CZT)催化剂,考察了CZT催化剂固相结构、酸量、比表面积等性能与催化活性的关系。采用XRD、BET、NH3-TPD、H2-TPR以及XPS等表征技术对催化剂进行表征。结果表明:焙烧温度为450℃时CZT催化剂具有最高的催化活性,其在240~400℃的温度窗口内活性均高于90%,且具有较好的抗水和抗硫中毒能力。随着焙烧温度的提高,催化剂表面的Ce和Zr原子进入体相晶格且Ce0.5Zr0.5O2向Ce0.75Zr0.25O2转变,导致催化剂的储释氧能力和氧化还原性能降低。另外,锐钛矿和金红石型TiO_2晶粒尺寸的增加,催化剂的有效比表面积和总酸量降低,因此CZT催化活性随着焙烧温度的提高而有所降低。换言之,大的比表面积、良好的氧化还原性能、表面Ce4+的富集以及酸性位的增多均有利于NH3-SCR活性的提高。     

Preparation and catalytic properties of ZrO2-Al2O3 composite oxide supported nickel catalysts for methane reforming with carbon dioxide

ZrO2-Al2O3 composite oxides and supported Ni catalysts were prepared, and characterized by N2 adsorption/desorption, X-ray diffraction (XRD) and X-ray photoelectron spectroscopy (XPS) techniques. The catalytic performance and carbon deposition was also investigated. This mesoporous composite oxide is shown to be a promising catalyst support. An increase in the catalytic activity and stability of methane and carbon dioxide reforming reaction was resulted from the zirconia addition, especially at 5wt% ZrO2 content. The Ni catalyst supported ZrO2-Al2O3 has a strong resistance to sintering and the carbon deposition in a relatively long-term reaction.     

纳米材料ZrO2颗粒液相吸附去除联苯胺研究

通过静态试验方法研究了ZrO2 纳米颗粒液相吸附联苯胺的性能 ,结果表明 ,虽然联苯胺均可与ZrO2 纳米颗粒表面羟基及水分子形成氢键 ,但它与ZrO2 纳米颗粒表面羟基之间形成的氢键稍强 ,吸附去除效果较好 ,该吸附体系很好吻合Freundlich和deBoer Zwikker吸附等温式 ,热分析显示联苯胺与ZrO2 纳米颗粒表面之间的吸附成键作用较弱。     

Cu/ZrO2/S2O2-8/γ-Al2O3固体酸催化剂制备与催化选择还原NO性能

以拟薄水铝石焙烧得到的γ-Al2O3为载体,分步浸渍负载（NH4）2S2O8、ZrOCl2和Cu（NO3）2,制成Cu/ZrO2/S2O28-/γ-Al2O3固体酸催化剂.考察了Cu/ZrO2/S2O8^2-/γ-Al2O3在富氧条件下对C3H6选择还原NO的催化性能,并借助SEM、XRD、Py-IR和TPR等表征方法研究了它的结构和性能的关系.性能的实验结果表明,Cu/ZrO2/S2O28-/γ-Al2O3在无水条件下能使NO的最大转化率达到82.9%,在有10%水蒸气存在条件下仍能使NO的最大转化率达到80.2%.表征测试的结果表明,S2O8^2-和ZrO2能够抑制γ-Al2O3颗粒之间的烧结及CuAl2O4尖晶石相的生成,同时促使催化剂表面新酸性中心（B酸）的形成及总酸量的增加,另外ZrO2还能提高Cu物种的还原性,从而有效地改善了催化剂的催化活性和水热稳定性.     

Die Bleisulfidhalogenide Pb2SJ2 und Pb2SBr2

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