动态晶化法合成N aP分子筛的研究

以硅酸钠和偏铝酸钠为原料,采用水热动态晶化法制备NaP分子筛,通过XRD,SEM,BET,PSD,FTIR表征手段对样品进行分析,考察了不同的硅铝比、晶化温度和动态转速对分子筛合成的影响,并对晶化过程进行了研究.结果表明在一定范围内提高初始原料的硅铝比、晶化温度、晶化时间和动态转速,有利于提高NaP分子筛的纯度.通过优化合成条件,在硅铝比为2.00,晶化温度为120℃,晶化时间为8 h,动态转速为70 r/min的条件下合成了粒径约为1.8μm的NaP分子筛.与静态晶化相比,动态晶化过程成核期较短,导致所需晶化时间显著降低,且合成产物具有较大的比表面积和孔径分布.     

以酸解正硅酸乙酯为硅源合成ZSM-5分子筛的过程调控

正硅酸乙酯（TEOS）作为合成ZSM-5分子筛的常用硅源,其在不同酸碱介质中水解的前驱体聚合状态对ZSM-5分子筛的粒径和孔径分布具有调控作用。以酸性介质TEOS水解缩合的前驱体为硅源,在水热条件下合成ZSM-5分子筛,并利用XRD、SEM、BET、FI-IR等方法对反应不同阶段的样品进行表征分析。主要考察了水解程度、水解时间、合成过程的pH、晶化温度、晶化时间及模板剂用量对ZSM-5分子筛合成过程的调控,结果表明：以乙醇为共溶剂,以TEOS在硫酸介质pH=2.0时水解20 h的前驱体为硅源,水热合成过程中加入模板剂四丙基氢氧化铵（TPAOH）,铝源为氢氧化铝,180 ℃晶化30 h合成了粒径约为200 nm的ZSM-5分子筛,其比表面积提高了35.6%,平均孔径降低了48.6%。     

复合分子筛β∕SBA-15的合成及表征

以β分子筛为部分硅铝源,正硅酸乙酯为硅源,P123为模板剂,采用后合成法在水热条件下制备复合分子筛β/SBA-15。考察了酸浓度、酸体积、晶化温度和晶化时间等合成条件对合成样品的影响。通过XRD、红外(FTIR)、N2吸附-脱附等表征手段对其结构进行了表征,结果表明,酸浓度为6 mol/L,酸体积40 mL,β加入量50%(占样品质量分数),晶化温度110℃,晶化时间48 h为最佳合成条件,β次级结构单元进入SBA-15孔壁中,孔壁变厚。然后,将Hβ、机械混合分子筛、复合样品的苯酚烷基化催化效果进行对比,表明合成样品优于机械混合型分子筛。     

硅源对纯硅MCM-41介孔分子筛结构性能的影响

分别采用正硅酸乙酯(TEOS)、气相法白炭黑、硅溶胶为硅源,十六烷基三乙基溴化铵(CTEAB)为结构导向剂,在100℃用水热晶化法在碱性(NaOH)介质中反应5d,合成出MCM-41介孔分子筛样品。通过XRD、N2吸附-脱附测试手段对不同硅源合成的样品进行了对比表征分析,实验结果表明,相对于TEOS作为硅源,气相法白炭黑和硅溶胶制得的MCM-41具有较大的孔径(>4nm)和孔容(>1cm3/g)以及高的比表面积(1000m2/g),在制备大孔径的介孔MCM-41时,气相法白炭黑和硅溶胶是两种比较好的硅源。     

含氟体系中合成条件对MCM-48分子筛结构性能的影响

在合成过程中引入F~-可以缩短MCM-48分子筛的晶化时间,考察以正硅酸乙酯(TEOS)为硅源、十二烷基三甲基溴化铵(CTAB)为模板剂的合成体系中加入F~-后,n(CTAB)∶n(Si)、晶化时间和晶化温度等合成条件对MCM-48结构性能的影响。XRD、N_2吸附脱附和TEM等表征结果表明,在n(CTAB)∶n(Si)=0.65、晶化温度120℃和反应时间24 h条件下,合成的MCM-48分子筛结晶度较高,比表面积为1 305 m~2·g~(-1),平均孔径3.416 nm,为MCM-48分子筛的适宜合成条件。     

介孔分子筛MSU-X合成条件对结构及热稳定性影响的XRD研究

以十八烷基聚氧乙烯醚(C18EO10)为模板剂,以正硅酸乙酯(TEOS)和硅酸钠分别为硅源,研究了不同pH值、反应温度、反应时间、原料比等条件下,合成的全硅MSU-X型介孔分子筛产物的结构变化规律,并通过焙烧和水热处理,考察了MSU-X介孔材料的结构稳定性.实验采用粉末多晶X射线衍射技术,分析了合成条件对MSU-X介孔分子筛结构和稳定性的影响.结果表明:以正硅酸乙酯为硅源,原料摩尔比为TEOS:C18EO10:H2O＝1:0.225:150,凝胶pH值为2,晶化温度为55℃,晶化时间48 h,相应的MSU-X材料具有较好的热稳定性和水热稳定性.相比之下,以硅酸钠为硅源得到的MSU-X材料,具有更高的短程有序度,孔壁厚、孔径小,稳定性优于以正硅酸乙酯为硅源合成的MSU-X产物,经900℃焙烧2 h或760℃水蒸气处理7 h后仍保持其孔道结构.     

自模板法制多级孔ZSM-5及其在MTA反应中的应用

以改良的Stober方法制得的介孔硅球为硅源兼硬模板剂,合成硅铝摩尔比为30的多级孔ZSM-5分子筛。采用XRD、FESEM、N_2吸附-脱附、NH_3-TPD等手段对合成的样品进行表征,研究晶化温度、晶化时间、晶化方法对分子筛形貌和结构性能的影响,并将其应用于甲醇制芳烃(Methonal to Aromatics,MTA)反应。结果表明,以介孔硅球作为硅源兼硬模板剂,在110℃条件下晶化72 h能够得到结晶度较高的ZSM-5分子筛,该分子筛含有丰富的介孔及大孔,比表面积高达529 m~2/g,且在MTA反应中表现出比较好的催化稳定性。     

中微双孔分子筛SBA-15的合成

采用P123(PEO20PPO70PEO20)为模板剂,正硅酸乙酯(TEOS)为硅源试剂,在强酸溶液中采用水热晶化法合成中微双孔分子筛SBA-15,并考察模板剂浓度、反应温度,离子导向剂和共溶剂对中微双孔分子筛SBA-15的影响.结果表明:控制合成温度可以精确调控SBA-15的介孔孔径;引入离子导向剂后合成的SBA-15具有更好的介孔有序性;加入共溶剂N,N-二甲基酰胺(DMF)会破坏SBA-15孔道的有序性,孔壁变薄,但可以提高分子筛的比表面积和孔容,大幅度提高孔径;采用乙醇后处理分子筛SBA-15有利于保持分子筛骨架.合成中微双孔分子筛SBA-15的合适条件为P123,TEOS,NaCl,HCl与H2O物质的量之比0.017∶1∶1.5∶9.86∶137,反应温度40℃,P123自组装反应时间4 h,与硅源组装老化时间24 h,晶化温度100℃,晶化48 h,在此条件下得到高质量的中微双孔分子筛SBA-15对苯吸附量接近1 000mg/g.     

高结晶度ETS-10分子筛的合成与表征

采用水热合成法成功合成出高结晶度ETS-10分子筛。通过XRD、N2吸附-脱附、FTIR、SEM和NMR等方法对样品进行了表征,并考察了不同合成条件对ETS-10分子筛结晶度的影响。结果表明,碱度、硅钛比、晶化时间对分子筛结晶度影响显著。在分子筛制备过程中,钛溶解分散于凝胶体系,并在晶化过程中完全进入分子筛形成Si-O-Ti骨架结构,是合成高结晶度ETS-10分子筛的关键。制备的ETS-10分子筛晶粒形状规整,比表面积高,无杂晶相,具有高的结晶度。     

偏高岭土水热合成磷酸硅铝分子筛及其表征

以具有一定活性的偏高岭土兼作铝源与硅源、正磷酸作磷源、三乙胺和氧氟酸为复合模板剂,用水热方法合成了磷酸硅铝分子筛(SAPO-5).利用X射线衍射分析、红外光谱分析、扫描电镜、Brunauer-Emmett-Teller分析等手段对产物进行了表征.研究了不同晶化时间对产物晶相组成的影响.在473 K下,晶化时间为24 h时,可得到结晶度较高的SAPO-5晶体,其形貌为尺寸大约200 nm的柱状晶体,比表面积为205.9 m2/g,平均孔径为9.72 nm,孔容为0.73 cm3/g,属于介孔材料.     

悬浮法聚苯乙烯的粒径和粒径分布

通过苯乙烯悬浮聚合,研究了搅拌转速、分散剂浓度、相比、釜径和桨型对聚苯乙烯粒径和粒径分布的影响,并确定了相应的关联式,为选择最佳操作条件和聚合反应器的设计提供依据.     

分子印迹聚合物微球的粒径尺寸及分布

印迹技术是近年来发展起来的基于模拟抗体-抗原相互作用原理的新技术,广泛应用于手性物质拆分、仿生传感器、固相萃取、抗体模拟等领域。悬浮聚合法是制备分子印迹聚合物微球最常用的方法,本文就影响悬浮聚合法制备分子印迹聚合物微球粒径尺寸及分布的因素进行了探讨。     

Y型气流式喷嘴的雾化滴径和滴径分布

索特平均滴径(SMD)和滴径分布是描述喷嘴雾化性能的主要指标.根据Y型喷嘴雾化过程的特征,提出了Y型喷嘴的液滴随机分裂模型,得到了SMD的表达式.考察了Y型喷嘴对氯化聚氯乙烯(CPVC)氯化液的雾化过程,利用Mastersizer2000型测粒仪测定了雾化滴径分布.关联了SMD的经验方程,得到了初次雾化平均滴径.采用液滴随机分裂模型模拟计算了雾化滴径分布,计算结果与实验结果吻合,说明模型和平均滴径方程可以用来预测Y型喷嘴的雾化性能.     

聚氨酯分散体粒径及粒径分布与粒径控制

介绍了聚氨酯分散体粒径与粒径分布概念、测定粒径的方法,分析探讨了分散体内在因素和外部因素对粒径的影响以及聚氨酯分散体的粒径控制。     

Atmospheric Size Distributions Measured by Differential Mobility Optical Particle Size Spectrometry

ABSTRACT

A differential mobility and optical particle size spectrometer (DMOPSS) was developed to measure ambient size distributions based on geometric particle diameter in the size range of 0.1 to 1.0 μm diameter. The DMOPSS consists of a high-flow differential mobility analyzer (HF-DMA) followed by an optical particle counter (OPC) and condensation nucleus counter (CNC) operating in parallel. The OPC and CNC sample monodisperse aerosol of known geometric diameter from the HF-DMA output or, alternatively, polydisperse aerosol with known dilution directly from the ambient air. The monodisperse samples are used to create time-dependent calibrations of the OPC, providing optical response versus geometric size for the ambient aerosol under study. The direct ambient measurements are then reduced, using this ambient-based calibration. A field test of the DMOPSS system was performed in the summer of 1992 at Meadview, Arizona, where more than 12,000 size spectra were collected; they consisted of roughly one-third direct ambient samples and two-thirds HF-DMA sized samples. Measured aerosol volumes and calculated particle scattering coefficients were strongly correlated with nephelometer measurements, with a mean scattering-to-volume ratio of 5 m²/cm³. With the ambient aerosol calibration, the measured aerosol volumes were 47% larger, and volume geometric mean diameters were 12% larger, than would have been obtained using a polystyrene latex calibration.     

Influence of Cluster Size Distribution on Cluster Size Dependent Catalytic Kinetics

Abstract  

A theoretical analysis of the influence of particle size distribution on observed TOF dependence on cluster size is presented for a two step catalytic cycle. Such mechanism can display different TOF behavior including maxima. In the later case simulations demonstrated broadening of TOF curves compared to an idealized case of very narrow PSD. However, for more often observed cases with smooth TOF increase or decrease with cluster size increase incorporation of particle size distribution in kinetic analysis is not required at least for often experimentally observed particle size distributions.     

Improved Determination of Bimodal Size Distributions from Measurements with Diffusional Size Classification

The size distribution of the unattached fraction of the short-lived radon progeny is reported in the literature to have a bimodal structure. Due to the weak size resolution of diffusional size classification, a wide variety of bimodal size distributions yields similar measurement results, obstructing the reconstruction of size distribution parameters from measured data. For example, it could be shown that although 2 of the commonly used nonlinear approximation algorithms per formed well for the reconstruction of a monomodal size distribution, the reproduc tion of parameters of a bimodal size distribution was unsatisfactory. In conse quence, a "random walk" approach is presented. The basic idea for this approach consists of probing the complete parameter space as an ideal method for locating the best set of parameters. Additionally, 2 steps are introduced for the reduction of computation time to render the ideal approach to an applicable method. The range of geometric standard deviations for the calculation was restricted to values between 1 and 5. The range of median diameters was limited according to the penetration functions of the diffusional samplers. This restricted volume of param eter space was subdivided into 10⁴ cells. During the calculation, cells with exceptionally large values of the minimization functional were eliminated from further computation. Compared to the results of EM and Simplex algorithms, this ''random walk'' method was able to retrieve parameters of both monomodal and bimodal size distributions with improved accuracy.     

Critical Grain Size/Preexisting Flaw Size Relations in Anisotropic Brittle Solids

A known solution for the critical condition of thermoelastic microcrack initiation is adopted to evaluate the extent of crack propagation after initiation and the arrest condition. It is shown that the critical temperature for crack initiation and the strength of thermoelastically anisotropic polycrystalline materials is not determined by the grain size only but also by the ratio of grain-to-flaw size. The variation of slopes in the strength-grain size plot is interpreted in terms of preexisting annular flaw-size change. The major implications of the analysis are discussed in relation to experimental results on a number of polycrystalline ceramics.