非晶态ZrO_2镶嵌的超细CeO_2催化HCl氧化

采用不同方法制备了铈锆复合氧化物催化剂用于催化HCl氧化反应。自发沉积策略制备的CeO_2@ZrO_2催化剂中,超细CeO_2纳米粒子均匀的镶嵌于非晶态ZrO_2中。CeO_2粒子显著的"尺寸效应"使得该催化剂具有更高的Ce~(3+)和氧空位浓度,而较高的Ce~(3+)和氧空位浓度使得催化剂具有优异的低温氧化还原性能和储释氧能力。催化性能测试表明,CeO_2@ZrO_2催化剂展现出最好的催化活性(1.90 gCl2·gcat~(-1)·h~(-1)),同时CeO_2粒子周围非晶态的ZrO_2阻碍CeO_2的高温烧结,提高了该催化剂的稳定性。     

SiO2-Al2O3玻纤载体负载CuO-CeO2对挥发性有机化合物催化燃烧性能研究

采用等体积共浸渍法制备了CuO-CeO₂整体式催化剂,评价了催化剂对乙酸乙酯、异丙醇及甲苯的催化燃烧性能。采用N₂吸附-脱附、X射线衍射（XRD）、氢气程序升温还原（H₂-TPR）、氨气程序升温脱附（NH₃-TPD）以及挥发性有机化合物脱附等手段对催化剂进行了表征。表征数据显示,氧化铜以高分散态均匀分散存在于载体表面,氧化铈则是小的纳米颗粒,氧化铈颗粒粒径随着Cu/Ce物质的量比的减小而增大。添加铈氧化物会显著增加总酸量,特别是路易斯酸酸位的量,同时增强了乙酸乙酯和异丙醇的吸附量,吸附量的增加提高了催化剂对乙酸乙酯和异丙醇的催化燃烧性能。从甲苯的催化燃烧实验可以看出,大量添加CeO₂稍微增加了甲苯的吸附容量,减弱了催化剂的还原性、降低了活性氧的含量,最终导致甲苯的低转化率。催化行为由氧化铜、氧化铈以及载体三者之间的共同作用决定,这三者的协同作用不仅影响着表面氧的活性同时影响着催化剂对甲苯的吸附能力。     

非晶态MnO_x/TiO_2催化剂的制备及其低温NH_3-SCR性能

采用自发沉积法、共沉淀法及浸渍法制备MnO_x/TiO_2催化剂,通过XRD、TEM、N2吸附-脱附、XPS、H_2-TPR、NH_3-TPD等一系列表征手段研究MnO_x/TiO_2催化剂的结构与性质,并考察MnO_x/TiO_2催化剂低温NH_3-SCR性能。结果表明,自发沉积法制备的MnO_x/Ti O2(s)催化剂具有完全非晶态结构,Mn和Ti之间存在强相互作用,较共沉淀法制备的MnO_x/TiO_2(c)及浸渍法制备的MnO_x/Ti O2(i)表现出更强的氧化还原能力。MnO_x/TiO_2(s)具有较高的比表面积、较多的表面酸量,有利于NH_3的吸附与活化。且表面高浓度的Mn4+离子及吸附氧,有利于将NO氧化为NO2,促进发生"fast-SCR"反应,进而使其表现出优异的低温脱硝性能。MnO_x/TiO_2(s)催化剂在150℃时NO的转化率高达92.8%,在150-350℃NO的转化率保持在90%以上,此外其还具备较强的抗H_2O和SO_2毒化能力。     

Ni-Mg复合催化剂催化裂解CH_4制氢动力学研究

基于定温热重实验,建立了甲烷催化裂解反应动力学模型和催化剂表面积炭失活动力学模型。其中,甲烷催化裂解动力学模型将初始产氢速率视为催化剂未积炭条件下的动力学基础数据;催化剂表面积炭失活动力学则基于甲烷催化裂解速率的降低。实验使用Ni-Mg复合催化剂,分别在535、585、635℃,甲烷分压10~4、2×10~4、3×10~4Pa条件下展开甲烷催化裂解动力学特性研究。结果表明,甲烷催化裂解的反应级数为0.5,活化能为82 k J/mol;Ni-Mg复合催化剂反应失活级数为0.5,催化剂失活活化能为118 k J/mol。实验条件下均制得了多壁碳纳米管。     

ZSM-5分子筛催化甲醇制汽油反应中的晶粒粒径效应研究

通过调控水热合成ZSM-5凝胶液中H_2O/Si物质的量比,实现了粒径为70、200、400和650 nm四种单分散ZSM-5的可控合成。采用XRD、TEM、BET和NH_3-TPD等多种表征对其微观结构进行分析,结合催化性能评价,考察了晶粒粒径对其催化甲醇制汽油反应性能的影响机制。结果表明,整体上随着ZSM-5晶粒粒径的增加,其外比表面积减小,结晶度提高,酸量呈现出先增加后基本不变的趋势。但外表面附着小晶粒的粒径为650 nm的分子筛体现出了大的外表面积和强的酸性。ZSM-5晶粒粒径的增加整体上降低了其催化MTG反应的寿命和最高收率。晶粒粒径为70 nm时,ZSM-5体现出了96 h的催化寿命和30.8%的最高收率。晶粒粒径为650 nm样品由于其大的外比表面积和较强的表面酸性,也体现出91 h的寿命。在大晶粒ZSM-5外表面附着生长小晶粒ZSM-5,是一种制备高性能催化剂的新方法。     

氮化SBA-16负载镍基催化剂的制备及其对甲烷二氧化碳重整反应的催化性能

通过软模板法合成了SBA-16分子筛,采用高温氨气氮化的方法使有序介孔硅材料中的氧原子部分被氮原子取代,得到氮化的SBA-16载体(SBA-16-N)。采用满孔浸渍法制备了镍基催化剂,并将制得的Ni/SBA-16和Ni/SBA-16-N催化剂用于甲烷二氧化碳重整反应。通过透射电镜、氮气物理吸附、X射线衍射、X射线光电子能谱和二氧化碳程序升温脱附等手段研究了载体和催化剂的结构,并利用热重分析对反应之后回收催化剂进行了表征。结果表明,高温氮化后的分子筛中掺入了氮元素,增加了载体的碱性,改善了载体对反应气体的吸附活化能力,增强了载体与金属之间的相互作用,从而提高了催化剂的活性和抗积炭性能。     

全二维气相色谱-飞行时间质谱对催化裂化汽油的定性与定量分析

采用全二维气相色谱-飞行时间质谱(GC×GC-TOF MS)对催化裂化汽油全馏分进行了定性与定量分析,建立了相应的分析方法.结果表明,汽油族组成中的烷烃、烯烃、环烷烃、芳烃在全二维点阵谱图中呈分区域、带状的分布特点.GC×GC-TOF MS根据催化裂化汽油组分内分子的沸点及极性差异对其进行两个维度分离,极大地避免了普通色谱法分析过程中沸点相似化合物共流的弊端,实现催化裂化汽油组分的精确分离和准确定性分析.通过引入响应因子,修正了不同性质的烃类在电离源上电离效率的差异,使得TOF对催化裂化汽油族组成的定量结果与普通气相色谱法的定量结果的相关性较好,且应用GC×GC-TOF MS方法获得了催化裂化汽油更为精确的族组成信息.GC×GC-TOF MS为催化裂化汽油精确表征提供了一种有效方法.     

Catalytic chain transfer polymerization of isobutylene: The role of nucleophilic impurities

Fast polymerization of isobutylene (IB) initiated by tert‐butyl chloride using ethylaluminum dichloride·bis(2‐chloroethyl) ether complex (T. Rajasekhar, J. Emert, R. Faust, Polym. Chem. 2017, 8, 2852) was drastically slowed down in the presence of impurities, such as propionic acid, acetone, methanol, and acetonitrile. The effect of impurities on the polymerization rate was neutralized by using two different approaches. First, addition of a small amount of iron trichloride (FeCl₃) scavenged the impurity and formed an insoluble · impurity complex in hexanes. The polymerization rate and exo‐olefin content were virtually identical to that obtained in the absence of impurities. Heterogeneous phase scavenger (FeCl₃) exhibited better performance than homogenous phase scavengers. In the second approach, conducting the polymerization in wet hexanes, the fast polymerization of IB was retained in the presence of impurities with a slight decrease in exo‐olefin content. ¹H NMR studies suggest that nucleophilic impurities are protonated in the presence of water, and thereby neutralized. Mechanistic studies suggest that the rate constant of activation (k_a), rate constant of propagation (k_p), and rate constant of β‐proton elimination (k_tr) are not affected by the presence of impurities. To account for the retardation of polymerization in the presence of impurities, delay of proton transfer to monomer in the chain transfer step is proposed. © 2017 Wiley Periodicals, Inc. J. Polym. Sci., Part A: Polym. Chem. 2017 , 55, 3697–3704     

Switchable solvent based liquid phase microextraction of palladium coupled with determination by flame atomic absorption spectrometry

A switchable solvent-based micro-extraction method for pre-concentration and separation of ultratrace palladium was developed prior to its flame atomic absorption spectrometric detection. Reverse change of hydrophilicity of N,N-dimethylcyclohexylamine (DMA) was achieved by reaction with carbonated water. The hydrophilic bicarbonate salt of the protonated DMA was used as extractant for palladium complexed with 2-(5-bromo-2-pyridylazo)-5-diethylaminophenol (5-Br-PADAP). Formation of the hydrophobic form of switchable solvent from hydrophilic form of switchable solvent phase was achieved by addition of sodium hydroxide into the extractant-sample solution. The effect of key parameters affected extraction recovery was studied and optimised by using Plackett–Burman design, central composite design and three dimension (3D) surfaces response. The calibration plot was linear in the range 0.015–1.6 mg L^?1 of palladium with a correlation coefficient of 0.999. The limit of detections values of palladium for liquid and solid samples were 4.28 μg L^?1 and 0.54 µg g^?1, respectively. The pre-concentration factor was 37.5. The accuracy was confirmed by determination of palladium in certified reference material. The procedure was also applied for determination of palladium content of real samples as automotive catalytic converter, roadside dust, sea water and river water.     

四氯化碳液相催化加氢制氯仿多元金属催化剂的制备及其催化性能

以贵金属M(=Pd,Pt)为主要活性成分,掺加过渡金属Fe和Ni作为助剂,采取浸渍和氢气还原法制备了椰壳活性炭(ACcs)负载的单元金属(M/ACcs)、二元金属(M-Ni/ACcs、M-Fe/ACcs)和三元金属(M-Ni-Fe/ACcs)系列催化剂;通过CC_l4液相催化加氢制氯仿反应考察了这些催化剂的催化活性和选择性。结果表明,Pd基催化剂的催化活性明显高于Pt基催化剂,但后者对氯仿的选择性优于前者;在前5 h加氢反应时段,两系列催化剂的活性顺序为:Pd-Ni-Fe/ACcsPd-Fe/ACcsPd/ACcsPd-Ni/ACcs和Pt/ACcs≈Pt-Fe/ACcsPt-Ni/ACcsPt-Ni-Fe/ACcs;总体上,引入Fe对于催化性能的改善效果要优于Ni,Ni的单独引入则会不同程度地降低催化活性。综合考量成本、活性和选择性等因素,优选Pd-Ni-Fe/ACcs作为催化剂,在393 K下反应5 h,可实现CC_l497.6%的转化率以及接近100%氯仿的选择性。