ZSM-5/Y复合结构分子筛的制备及其复合结构形成机制的探索

以工业ZSM 5分子筛作为硅源,采用水热法制备ZSM-5/Y复合结构分子筛,并对其进行了X射线衍射(XRD)、N2吸附(BET)、核磁共振(NMR)和扫描电镜(SEM)表征.结果表明,产物同时具有ZSM-5分子筛和Y型分子筛的晶相结构特征.晶种的加入能有效地提高晶化反应进程.NaOH溶液的碱性越高,对ZSM-5的溶解性越高.随着晶化时间的延长,属于ZSM-5分子筛的特征峰强度降低、Y分子筛的特征峰强度升高.在晶化时间为10、20和30h时,对体系中加入铝源和晶种进行了研究.结果发现,复合结构分子筛的合成过程伴随着分子筛上骨架硅解离、部分骨架铝解离、硅源和铝源在分子筛骨架外及骨架上晶化形成新的晶体的过程.推断ZSM-5/Y复合结构分子筛形成机制有两种:(1)铝源和溶液中溶解的硅结合;(2)铝源直接和ZSM-5分子筛骨架上的硅结合.     

Bi-MSU-4分子筛合成、结构及催化性能的研究

以聚氧乙烯失水山梨醇酸酯(Tween-x,x=20、40、60、80)为模板剂,正硅酸乙酯为硅源,在室温条件下首次合成了含有骨架金属元素铋的介孔分子筛T-20、40、60、80Bi-MSU-4.采用X射线衍射、傅里叶变换红外光谱、紫外-可见吸收光谱、低温N2吸附/脱附,扫描电镜等手段对样品进行表征,分别考察了模板剂种类、矿化剂、硅铋摩尔比等因素对分子筛结构、骨架形成及催化活性的影响.结果表明,Bi-MSU-4系列具有介孔分子筛典型形貌特征,且金属铋较好地分散于分子筛骨架中.样品的孔径与孔容随模板剂憎水链长度增加而增大,催化活性也相应提高;NaF的矿化作用可促进骨架的成型与脱落;随硅铋摩尔比增加,催化活性先增后减.在苯乙烯氧化反应中,T-xBi-MSU-4有优越的催化性能,其中T60Bi-MSU-4的苯乙烯转化率55.0%,苯甲醛产率41.5%.     

金属掺杂介孔氧化锆的合成与表征

采用直接合成法在非水溶剂中成功合成了分别由锌、镁等元素掺杂改性的介孔氧化锆分子筛,并用XRD、N2吸附-脱附、NH3-TPD等方法对其进行表征,还考察了影响合成的一些因素。结果表明,金属元素能够均匀地掺杂于介孔氧化锆的晶体骨架中。金属的掺入增加了介孔材料的热稳定性,但其骨架有所收缩,降低了有序度;络合剂三乙醇胺的加入增加了材料的热稳定性;模板剂P123的使用增加了介孔分子筛的有序度;金属的掺杂使得介孔分子筛制备的固体超强酸的酸位增多,酸度增强。     

碱处理对5A分子筛孔结构和氢吸附行为的影响

采用SEM、EDS、BET和气相色谱等分析方法,研究了NaOH碱处理对5A分子筛显微形貌、成分、比表面积、孔容和氢吸附性能的影响。结果表明,NaOH碱处理降低了5A分子筛骨架中硅铝比,增大分子筛比表面积、孔容和平均孔径,提高了分子筛活化温度。在77K温度及100KPa压力下,碱处理5A分子筛对含0.1vol%H2/He混合气体吸附后尾气氢浓度小于1ppm,氢吸附容量为6.9ml/g。碱处理增加了5A分子筛介孔数量和比表面积及平均孔径,但因为孔径增大,吸附中心周围阳离子对H2分子的作用减弱,碱处理5A分子筛低分压氢吸附容量并无增加。     

VTS-2分子筛的合成、表征与催化氧化性能

分别以TBOT、VOSO4.3H2O、TEOS为钛源、钒源和硅源,TBAOH为模板剂,异丙醇为溶剂,采用水热晶化法,在Si/(Ti+V)≥33(凝胶中)条件下合成了具有MEL拓扑结构,骨架含两种不同价态过渡金属钛、钒的杂原子分子筛VTS-2。采用XRD、FT-IR、UV-Vis、EDS及催化反应等方法测试了所合成分子筛的晶相结构、波谱性质和催化氧化性能。对苯乙烯催化氧化反应的评价结果显示,在骨架金属含量相近的情况下,骨架含钛、钒两种过渡金属的VTS-2分子筛对烯烃的催化氧化活性分别高于骨架含单一金属的TS-2和VS-2,表明金属钒的引入有助于提高TS-2分子筛的催化氧化活性,调节氧化产物分布。     

活化凹凸棒石合成多级孔钛硅分子筛及其光催化性能研究EI北大核心CSCD

以天然凹凸棒石为硅源,钛酸丁酯为钛源,四丙基氢氧化铵为模板剂一步水热合成钛硅分子筛,并研究了钛硅比对合成产物结构和性能的影响。通过XRD,SEM,UV-Vis和N_(2)吸附-脱附对钛硅分子筛的晶体结构、形貌、钛的存在形式和孔道特征进行表征,并对亚甲基蓝印染废水进行光催化实验考察分子筛的光催化性能。结果表明,当钛硅比为1∶30时,其XRD特征峰强,结晶度高,晶粒大小均匀,呈规则六棱柱状,钛以骨架钛和锐钛矿型TiO_(2)形式存在,孔道结构兼具微孔和介孔。分子筛具有光催化性,光催化反应遵循拟一级反应动力学。利用响应曲面法建立模型优化pH=7.8亚甲基蓝溶液最佳实验条件为初始浓度10.0 g/mL,光催化时间48 min,投加量0.05 g,经光催化降解溶液脱色率达到98.75%。     

硅铝分子筛骨架脱铝模型

通过把硅铝分子筛的骨架脱铝过程简化为分子筛骨架中杂原子的扩散和空位的形成及迁移过程,使用费克第二定律建立扩散方程,得到任意时刻铝原子的浓度关于位置的函数,并讨论了影响脱铝的几个重要因素.用XPS、红外光谱和27Al-NMR测定在一定条件下处理后的氢型丝光沸石和ZSM-5的骨架硅铝比的变化,并与由所建立的数学模型计算出的骨架硅铝比比较,验证了公式的准确性.     

液相硅沉积改性HZSM-5分子筛的择形吸附分离性能研究

以聚硅氧烷作为改性剂,通过液相硅沉积表面修饰对HZSM-5分子筛吸附剂进行了择形功能化改性,采用X射线衍射(XRD)、NH3-TPD、比表面积与孔径分析和热重分析(TGA)等手段对改性前后的吸附剂进行了表征。分别采用液相吸附法和气相吸附法研究了ZSM-5择形分子筛对于对二甲苯(pX)和间二甲苯(mX)混合物的择形吸附分离效果,考察了硅沉积改性程度、液相吸附及气相吸附工艺条件对硅沉积修饰分子筛Si/ZSM-5择形吸附分离性能的影响。研究结果表明,分子筛吸附剂中介孔体积随着硅沉积改性次数增加而减少,而微孔体积改变较小,但4次硅改性后的分子筛吸附剂的晶体结构未发生明显变化。同时,随着硅沉积改性次数的增加,分子筛吸附剂的吸附量减小,而吸附剂的择形吸附分离系数βpX/mX增大;另一方面,气相热解吸得到的pX/mX选择性高于液相解吸法,并且二氯甲烷作为液相解析剂的pX/mX择形选择性高于甲苯和环己烷解析剂。吸附重量动态分析测试结果表明,Si/ZSM-5(0)、Si/ZSM-5(2)和Si/ZSM-5(4)的平均吸附容量分别为102.1,82.12和71.84mg/g,pXmX二甲苯混合物的扩散速率随着硅沉积改性程度的增加而明显减小。     

双模板剂B-EU-1/ZSM-5复合分子筛的快速合成及催化应用

以不同氢氧化物做碱源合成B-EU-1/ZSM-5复合分子筛, 并比较各平衡阳离子的结构导向作用及其形貌特征, 发现钠离子的导向作用最强, 且合成复合分子筛的表面较光滑、无明显晶面界限。对合成样品进行了TG-DTG、N₂吸附-脱附和NH₃-TPD分析。结果表明: 双模板剂一步法合成的复合分子筛模板剂脱除的失重率为5.67%, 小于机械复合分子筛的失重率7.31%, 复合分子筛的比表面积、孔容和微孔平均孔径均有所增大, 同时其酸强度、酸量都增大, 有利于二甲苯优先从复合分子筛的孔道结构中扩散出来。将分子筛应用于甲醇转化制二甲苯催化反应, 结果显示, 双模板剂一步法合成的复合分子筛催化产物油相中芳烃的选择性最高达到66.72%, 芳烃中二甲苯的含量为46.15%, 二甲苯中对二甲苯的含量达到30.75%。这是由于B-EU-1/ZSM-5催化剂的特殊孔道结构具备择形效应, 使得分子动力学直径较小的二甲苯分子优先从其孔道中扩散出来。     

二乙烯三胺五甲叉膦酸锆对铀吸附性能的研究

采用二乙烯三胺五甲叉膦酸(DTPMP)为有机膦源,以氧氯化锆(ZrOCl₂·8H₂O)为无机锆源,使用水热法制备了二乙烯三胺五甲叉膦酸锆有机杂化材料(Zr-DTPMP)。其后通过红外光谱、扫描电镜和X射线能谱等手段对不同膦锆配比下合成的有机-无机杂化材料进行了表征,同时将铀(Ⅵ)溶液初始pH、接触时间、铀初始浓度、温度和吸附剂投加量等作为影响因素对有机膦酸锆(Zr-DTPMP)对吸附铀(Ⅵ)性能的影响做出静态吸附法研究。结果表明:Zr-DTPMP的红外谱图中出现了P—O—Zr和C—P的伸缩振动,表明成功制备了有机杂化材料,且扫描电镜结果显示其表面具有丰富的孔结构。吸附后Zr-DTPMP的能谱图中出现了铀的能量散射峰,证实了Zr-DTPMP可去除水溶液中的铀(Ⅵ);在吸附实验中,Zr-DTPMP吸附铀(Ⅵ)的最佳条件为膦锆比为5∶1,pH=4.0,吸附平衡时间为360min,铀初始浓度为50mg/L,温度为298K,投加量为0.01g。     

Insertion of triangulated surfaces into a meccano tetrahedral discretization by means of mesh refinement and optimization procedures

In this paper, we present a new method for inserting several triangulated surfaces into an existing tetrahedral mesh generated by the meccano method. The result is a conformal mesh where each inserted surface is approximated by a set of faces of the final tetrahedral mesh. First, the tetrahedral mesh is refined around the inserted surfaces to capture their geometric features. Second, each immersed surface is approximated by a set of faces from the tetrahedral mesh. Third, following a novel approach, the nodes of the approximated surfaces are mapped to the corresponding immersed surface. Fourth, we untangle and smooth the mesh by optimizing a regularized shape distortion measure for tetrahedral elements in which we move all the nodes of the mesh, restricting the movement of the edge and surface nodes along the corresponding entity they belong to. The refining process allows approximating the immersed surface for any initial meccano tetrahedral mesh. Moreover, the proposed projection method avoids computational expensive geometric projections. Finally, the applied simultaneous untangling and smoothing process delivers a high‐quality mesh and ensures that the immersed surfaces are interpolated. Several examples are presented to assess the properties of the proposed method.     

From Industry 4.0 to Research 4.0. Development of High Performance Fibers in the Light of Digitization

We associate a variety of innovations with the term ＂Industry 4.0＂. The pioneer of many 4.0 modifications forms the basisfor the trend towards the integrated di...     

The Research of Anti-Wear Properties of Organomolybdenum Compounds in the Engine Oils

A four-ball tester was used to evaluate the anti-wear performance of three kinds of organomolybdemun compounds in the engine oils, i. e., molybdenum dialkyldithiophosphate (MoDDP), molybdenum dialkyldithiocarbamate ( MoDTC), and sulphur and phosphorus freeorganomolybdeum (Molybdate). The results indicate that a low concentration of MoDDP doesn' t improve the anti-wear properties of the commercial engine oils, but a high concentration of MoDDP can obviously improve the anti-wear properties and the load-carrying capacity of the engine oils. MoDTC doesn' t improve the antiwear properties of the engine oils, but worsens the anti-wear properties of the oils. Signifi can timprove ment of frictional and wear characteristics is obtained with Molybdate added in the commercial engine oils and the formulated oils.     

Roman iron and steel: A review

ABSTRACT

The production of ferrous metal increased during the Roman Late Republican period, Principate and Empire. The direct bloomery process was used to extract the metal from its ores using slag-tapping and slag-pit furnaces. The fuel was charcoal and an air blast was introduced by bellows-operated tuyères. Iron formed as a bloom, often as a spongy mass of metal, which contained impurities from the smelting process, including unreacted ore, fuel, slag and fragments from the furnace walls, while the metal was often inhomogeneous with varied carbon contents. Blooms were either smithed directly into bars or ingots or they were broken up, which also allowed the removal of gross impurities and a selection of pieces with similar properties to be made. These could then be forge-welded together and formed into characteristically shaped ingots. Making steel in the furnace seems to have been achieved: it depended on the ore and the furnace and conditions within it. Surface carburization was also carried out. Iron and steel were used extensively in construction and for tools and weapons. Fire welding was often used to add pieces of steel to make the edges of tools and weapons, which could be heat-treated by quenching to harden them.     

Certification Institutions Expected to Update and Transfer Information on Present Standards

Standards are the basis for production enterprises to organize production, ex-factory inspection, trade (delivery) and technical exchanges, product certification, quality arbitration and supervision.……     

Flow calorimeter for enthalpy increment measurements on condensed gases

A flow calorimeter for enthalpy increment measurements on condensed gases is presented. A better knowledge of the properties of the liquefied natural gas is needed, and therefore a liquid loop has been designed for our flow calorimeter. The fluid loop in the calorimeter is designed in order to avoid the two-phase region, since two phases would give compositional disturbances in the measurements. The avoidance of the two-phase region is made possible by increasing the pressure of the test fluid after the measurement section, then heating the fluid at super-critical pressure past the critical point. Finally, the fluid is throttled to the low-pressure gas state at the inlet condition of the compressor that circulates the fluid. To perform the pressure increase, a new cryogenic pump has been designed. To evaluate the new equipment, measurements were taken on liquid ethane over the temperature range 146–256 K at pressure between 0.9 and 5.1 MPa.     

Certification Becomes Important for the I Quality; and Safety Supervision of the Chinese Liquor Sector

The end of 2007, over 200 unit products of more than 80 Chinese firms have passed the quality grade certification for liquor products. These products involve distilled spirits, beer, wine, yellow wine, fruit syrup wine and others, and cover over 80% of the national top-branded liquor products.……     

Deposition and Coating Properties on CVD Tungsten

Surface characterization and microstructure studies are performed on chemical vapor deposited (CVD) tungsten coating. There is about 2 μm thickness diffusion layer of tungsten in the molybdenum substrate. The thermal shock test shows tungsten coating has good adhesion with molybdenum substrate, but the elements of oxygen and carbon in the tungsten coating have the bad affection to the adhesion. The result of high-temperature diffusion experiment is the diffusion rate from molybdenum substrate to tungsten coating is faster.     

Synthesis of Alumina-Zirconia Nanocomposites by Solgel Process

Al₂O₃-ZrO₂ nanocomposites were developed starting with the solgel process. Composite alumina-zirconia nanopowders were synthesized from metallorganic precursors (Aluminium secondary butoxide and zirconium Iso propoxide) using the solgel process. The parameters affecting the synthesis—solvent, concentration of precursor, R/H ratio (i.e., dilution of water in solvent)—were varied as also the temperature and pH. BET and TEM were used to measure nanosize. Diffuse reflectance spectroscopy and also qualitative optical absorption led to identical particle size estimate. The variation of process parameters was used to study the effect and interdependence of process parameters. Artificial Neural Networks was used to rigorously analyze the process. Although this led to confirmation of interdependence of parameters, the presence of a single overwhelming solvent variable was also established. Then the optimal process was used to synthesize more nanopowder. To produce bulk nanocomposite the nanopowders were sintered by varying the temperature and time period. The sintered lithoids were probed with a vickers hardness tester to measure elastic modulus, hardness, and fracture toughness. The results showed high elastic modulus, modest hardness, and very high fracture toughness.