酸碱性浸渍条件对钯炭催化剂加氢性能的影响

采用氢氧化钠和盐酸调节钯炭(Pd/C)催化剂制备过程中的浸渍液的pH,制备了相应的钯炭催化剂。对Pd/C催化剂的成分、形貌等性质进行表征分析,研究了不同浸渍条件下制备的Pd/C催化剂对苯甲醛和2-氰基吡啶加氢的催化性能。结果表明,酸/碱浸渍方法可有效控制钯颗粒的尺寸大小及分散度。在浸渍液的pH值为3的条件下制备出的Pd/C-1~#催化剂平均粒径为2.78 nm。当浸渍液的pH值为10时,制备的Pd/C-2~#催化剂平均粒径为3.75 nm。对于2-氰基吡啶加氢,采用酸性浸渍条件制备的Pd/C催化剂具有更好的催化效果;而采用碱性浸渍条件制备的Pd/C-2~#催化剂对苯甲醛加氢效果更好。     

糠醛液相脱羰用Pd/γ-Al2O3催化剂制备新工艺研究及活性评价

采用浸渍沉淀法制备了糠醛液相脱羰用Pd/Υ-Al2O3催化剂,讨论了浸渍初始液pH、加入载体后浸渍液pH、还原时pH、浸渍时间对催化剂活性的影响,确定了最佳的制备条件为:浸渍初始液pH=1;加入载体后浸渍液pH =7;还原时pH =8;浸渍时间=60 min.X射线衍射表征结果显示,催化剂中的钯以零价态存在,透射电镜分...     

金属蜂窝负载Pd催化甲烷部分氧化制合成气

采用浸渍法制备负载金属Pd(其中金属Pd含量0.6g/L)活性组分的金属蜂窝载体催化剂,应用于甲烷部分氧化制合成气。实验表明,焙烧温度为950℃的催化剂较600℃的催化剂甲烷转化率、CO和H2的选择性更高,焙烧温度为950℃的催化剂在反应温度800℃,GHSV=1×105ml/g·h条件下,甲烷转化率为91%,CO和H2的选择性分别达到90%和89%。用SEM与XPS对催化剂进行表征,结果表明,950℃焙烧催化剂并没有出现明显的烧结现象,且可能由于更多零价Pd的出现,使得该催化剂的性能更好。由于金属蜂窝载体优良的导热性,对950℃焙烧温度制备的金属蜂窝催化剂,催化剂床层的飞温点温度小于880℃,可以解决其它类型催化剂在甲烷部分氧化反应中出现的飞温问题,具有一定的工业化意义。     

用乙酰丙酮钯作前驱物制备Pd/C催化剂的研究

分别采用乙酰丙酮钯、氯化钯和硝酸钯作前驱物,用浸渍-还原法制备了一系列Pd/C催化剂,以松香歧化反应评价其活性,研究了活性炭类型、载体预处理、溶剂、还原方法及温度等因素对Pd/C催化剂活性的影响.结果表明,采用具有较大比表面积和孔容的活性炭作载体有利于钯在其表面的均匀分布和催化剂活性的提高;以Pd(acac)2作前驱体,以及使用极性较强的溶剂与用无机配合物前驱体相比,制备的Pd/C催化剂活性较高;TG-DTA分析表明Pd(acac)2在350℃下完全分解,基于此结果,作者在350℃条件下采用氢气干法还原,制备出活性略高于从日本进口的Pd/C催化剂.     

还原制备时的pH值对Pd/C催化剂性能的影响

采用液相还原法,以甲酸为还原剂制备了负载量为5%的Pd/C催化剂。考察了还原过程中p H值对Pd/C上硝基苯液相催化加氢性能的影响,并用XRD、SEM、TEM等手段对催化剂的结构进行了表征。结果表明,制备过程中随着p H的增大,催化剂活性先增大后减小;适宜的p H值能加快Pd还原反应的速率,有利于粒子快速成核,降低生成大粒径Pd粒子的几率,减少团聚,使Pd粒子均匀分散在活性炭载体上,获得较高的催化活性。p H=9时制得的催化剂上Pd晶粒分布均匀,平均粒径为3.63 nm;在50℃、H2压力0.8 MPa、搅拌速率100 r/min,反应45 min的条件下,这一催化剂对硝基苯加氢液相催化为苯胺的转化频率(TOF)达到8758 h-1。     

La、Ba的添加对Pd/Y2O3-ZrO2催化氧化CH4性能的影响

以浸渍法制备了1.0%Pd/Y2O3-ZrO2催化剂,考察了Pd负载过程中La和Ba的添加对Pd/Y-ZrO2催化氧化CH4性能的影响,用BET、XRD、CO脉冲、TEM和H2-TPR等方法对所制备的催化剂进行表征。结果表明,La和Ba的添加降低了Pd/Y2O3-ZrO2催化剂氧化CH4的活性。催化剂中活性金属的分散度及体相PdO的还原性影响催化剂对CH4的氧化活性,La、Ba的添加降低了Pd/Y2O3-ZrO2催化剂中活性金属Pd的分散性,使Pd在高温老化后更容易团聚,同时增强了PdO与载体的相互作用,使PdO不容易被还原。     

自制六通道反应器用于评价蒽醌加氢Pd/Al2O3催化剂

自制了六通道固定床反应器,以蒽醌加氢为测试反应研究了该反应器的实用性。测试结果表明,该反应器各平行反应通道的相对误差小于3%。利用该反应器进行了蒽醌加氢Pd/Al2O3催化剂研究,考察了浸渍浓度、焙烧温度对催化剂加氢性能的影响,得到Pd粒子最佳浸渍浓度为1.2 g/L,适宜焙烧温度为450℃,催化剂氢效8.29 g/L,选择性97.2%。     

Ru/Mn-Ce/TiO2及Ru/TiO2催化剂对丁二酸的催化湿式氧化研究

采用浸渍法制备了2个系列的Ru／Mn-Ce/TiO2及Ru/TiO2催化剂,并用XRD、TEM、BET等方法对催化剂进行表征。在T=270℃和Po2=1．5MPa条件下,在间歇式反应釜中对丁二酸进行降解实验。结果表明60min内丁二酸降解的总有机碳(TOC)去除率为80％～99．8％;在钌含量相同的情况下,Ru／Mn-Ce／TiO2催化剂的催化活性高于Ru/TiO2催化剂;Ru含量较低的情况下,Mn、Ce对提高催化活性有很大作用,但Ru含量增加时Mn、Ce的作用减弱;氢还原的温度对Ru/TiO2系列催化剂的催化氧化活性有明显影响,500℃还原钌所得催化剂对丁二酸的催化氧化活性优于350℃。     

La-Pd负载工艺对单Pd三元催化剂起燃性能的影响

通过Pd的预还原和La-Pd共浸渍工艺制备了不同单Pd三元催化剂。通过CO化学吸附、XRD、TEM、H_2-TPR和起燃测试等表征手段,综合考察了Pd/Al_2O_3体系下Pd的预还原和La-Pd共浸渍工艺对其起燃性能的影响。试验结果表明,模拟气氛老化后,La-Pd/Al_2O_3-R催化剂表现出了较高的CO/NO_x/HC起燃活性。这主要是因为贵金属Pd的预还原和La-Pd共浸渍工艺相结合有利于在老化过程中形成活性较高的PdO_x/Pd物质。     

液相还原法制备新型Ru／C催化剂的研究

用正交实验考察了溶液温度、pH值、搅拌速度等因素对催化剂吸附量的影响规律，并据此用浸渍及甲醛还原法制备了系列Ru／C催化剂，在0．5MPa、120℃下测得葡萄糖加氢生成山梨醇的催化活性、山梨醇选择性和催化剂的稳定性。并运用程序升温还原TPR（temperatureprogrammedreduction）技术研究了催化剂的表面还原性质。结果表明：钌的负载量对Ru／C催化剂的性能影响较大，钌负载量为5％时，制得的催化剂具有较佳的各项性能。钌的负载量越少时，负载钌的分散度越高，钌与载体间作用力越强，催化剂的还原温度越高。同时，随着含钌量的增加，催化剂的还原峰发生明显的变化，负载量为5％时出现了明显的肩峰，化学吸附是催化活性的主要来源。     

Influence of the structure of TiO2, CeO2, and CeO2-TiO2 supports on the activity of Ru catalysts in the catalytic wet air oxidation of acetic acid

Ru catalysts, supported on TiO 2 , CeO 2 , and CeO 2 -TiO 2 , were prepared by the impregnation method. The effect of the structure of the supports on the activity of Ru catalysts was investigated in the catalytic wet air oxidation (CWAO) of acetic acid under 230℃ and 5 MPa in a batch reactor. Physical properties including the surface area, crystalline phase, and surface components of the Ru catalysts were characterized by N 2 adsorption, X-ray powder diffraction (XRD), and X-ray photoelectron spectroscopy ...     

Selective catalytic NOx reduction on Antimony promoted V2O5-Sb/TiO2 catalyst

Quantum chemical calculation was carried out to choose a promoter which can reduce the poisoning of V2O5/TiO2 catalysts by SO2.Several atoms were chosen as candidates and new catalysts were synthesized by impregnation method.The NOx conversion rate was measured at temperatures between 100 and 400 ℃ and poisoning effect was investigated.The most promising candidate promoter, Se, was excluded because of its high vapor pressure.On the other hand, Sb shows best promoting properties.Sb promoted catalyst reaches the maximum NOx conversion rate at 250 ℃.It also shows considerably enhanced resistance to poisoning of V2O5/TiO2 catalysts by SO2.     

BaO对单Pd催化剂净化甲醇燃料车尾气性能的影响

利用FIB/SEM切片、XRD、TEM和EDX、EELS等先进分析技术对微球模板法所制备的Au/Ag泡沫材料的微观结构、形貌、成分及成分分布等进行了细致的研究.结果表明:由微球状Au/Ag球壳堆积而成的泡沫材料中微球直径约8 μm,微球壁厚200～1200 nm; Au/Ag泡沫材料的球壳可细分为3层,内层和外层为Au/Ag合金的微粒,中间主要是非晶碳层,夹杂有少量的Au/Ag微粒;Au/Ag泡沫材料的骨架由单个空心球壳组成,球壳之间通过接触点的金属镀层连接在一起;球壳上有小孔状结构,是在热分解法去除聚苯乙烯微球模板对形成的;球壳壁厚分布不均匀,少数球壳有塌陷、变形、破裂等现象.这些详细的分析有助于改进工艺,提高Au/Ag泡沫材料的制备质量.     

Study on SCR De NOx mechanism through in situ electrical conductivity measurements on V2O5-WO3/TiO2 catalysts

V2O5-WO3/TiO2 catalysts were prepared by impregnation method and in situ electrical conductivity measurements were carried out to investigate the reaction mechanism for ammonia SCR (selective catalytic reduction) of NOx.The electrical conductivity change with ammonia supply and the increase of electrical conductivity were mainly caused by reduction of the labile surface oxygen.The electrical conductivity change of catalysts shows close relationship with the conversion rate of NOx.Variation of conversion rate in atmosphere without gaseous oxygen also supports that the labile lattice oxygen is indispensable in the initial stage of the de NOx reaction.These results suggest that the liable lattice oxygen acts decisive role in the de NOx mechanism.They also support that De NOx reaction occurs through the Eley-Rideal type mechanism.The amount of labile oxygen can be estimated from the measurement of electrical conductivity change for catalysts with ammonia supply.     

稀土与过渡金属改性TiO_2光催化降解甲基橙研究

采用溶胶-凝胶法制备稀土La和过渡金属Fe掺杂改性的Ti O2光催化剂用于降解甲基橙染料溶液,并借助X射线衍射(XRD)仪、X射线光电子能谱(XPS)以及固体光致发光光谱(PL)等测试技术对催化剂进行表征,研究La和Fe掺杂对Ti O2催化剂结构和光催化性能的影响规律。结果表明,掺杂稀土元素La、过渡金属Fe可有效降低Ti O2光催化剂的晶粒尺寸,提高锐钛矿相的含量,催化剂中均匀分散的镧物种、铁物种会增加Ti O2催化剂表面氧空位和缺陷浓度,Fe、La掺杂后Ti O2光催化剂对甲基橙的降解率分别提高约16%和约22%,且稀土La改性催化剂显示较好的循环稳定性。     

Double-stage poly-o-phenylenediamine modification with palladium nanoparticles

Accumulation of palladium ions in poly-o-phenylenediamine (PPD) redox polymeric matrix was studied by means of cyclic voltammetry (CVA), X-ray photoelectron spectroscopy (XPS), atomic force microscopy (AFM), and spectroelectrochemistry. CVA and XPS studies demonstrated nitrogen atoms binding palladium cations upon impregnation of PPD film with palladium chloride solution. Higher residual reduced or partially reduced PPD form of cathodic polymer doping was shown to increase the number of palladium cations in the polymeric matrix. AFM recorded a significant effect produced to the film surface structure by intercalation of both palladium cations and metal formed by reduction of cations.     

汽车尾气净化Pd催化剂的研究现状、进展及展望

阐述了汽车尾气净化Pd催化剂的技术特点、现状及展望,分析了Al2O3、稀土氧化物对汽车尾气净化Pd催化剂性能的影响,对比了不同制备方法的优异性,讨论了单Pd催化剂的可行性和实用价值,以及未来的研究方向、技术难点和热点.     

Physicochemical properties of palladium adsorbents as catalysts in liquid-phase hydrogenation

The structure and physicochemical properties of palladium catalysts used in liquid-phase hydrogenation processes were studied with the use of adsorption, calorimetric, thermogravimetry, and temperature-programmed reduction techniques. The specific surface areas and average sizes and volume of pores of the adsorbents were determined. The palladium on activated carbon catalysts was found to possess a complex porous structure, whereas palladium on combined alumina and coal carrier catalysts is an adsorbent with a nonporous structure. The concentration of the applied metal and the nature of a support have a significant impact on the physicochemical properties of palladium catalysts.