含铁沸石分子筛中硅铝比的测定

针对含铁沸石分子筛,提出用硅钼蓝光度法测硅,用EDTA和硝酸铅滴定法测铝铁合量,再用磺基水杨酸光度法测铁,根据测试结果计算硅、铝、铁的含量及求出硅铝物质的量比,并通过实验证明该方法简单可行。通过硅铝物质的量比的测定,能为分子筛产品的性能提供重要参考指标和理论依据,而且,根据实际需要,还可调整沸石的硅铝物质的量比,来满足所需性能。另外,本方法因为所需化学药剂常见,在一般实验室均可进行,所以在经济上和适用范围上都有较明显的优势,参考价值显著。     

Variation of the Si/Al ratio in nanosized zeolite Beta crystals

Zeolite Beta nanocrystals were prepared from basic aluminosilicate precursor solutions upon hydrothermal treatment at 100 °C. The Si/Al ratio of the initial system was systematically changed from 25 to infinity in order to study the limits in the framework composition of BEA-type crystallites synthesized from clear basic solutions. Furthermore, the effect of the Si/Al ratio on the precursor species, ultimate crystal size, morphology and yield was investigated. The results revealed that the crystallization kinetics of nanosized Beta are dependent on the amount of Al in the precursor solutions, that is, the nucleation and growth processes are faster in Al-rich systems. The crystallization process of zeolite Beta with Si/Al ratios in the initial solutions of 14, 23 and 32 was accomplished within 72 h, whereas longer crystallization times, 140 and 264 h, were necessary to obtain crystalline products with Si/Al ratios of 42 and infinity, respectively. The intermediates and final products were investigated by complementary techniques such as XRD, HRTEM, DLS, IR, NMR spectroscopy and chemical analysis. Low temperature (77 K) CO adsorption infrared spectroscopy was used to study the Brønsted acidity of zeolite Beta samples with different Si/Al ratios. The properties of Beta nanocrystals important for the design of catalysts and selective separation materials are provided based on the results obtained from the detailed characterization.     

低硅铝比X分子筛合成研究进展

综述了低硅铝比X分子筛合成的研究进展,分别从常规化学药品原料、非常规原料高岭土和其他原料进行了评述,并分析了各种原料和合成方法的优缺点,详细介绍了常规原料合成低硅铝比X分子筛的几种方法,重点讨论了在钾钠体系下低温老化高温晶化两步法合成低硅铝比X分子筛的研究进展,指出了高岭土和常规原料合成低硅铝比X分子筛存在物料不纯、活性不足、预处理工序复杂问题和不足。     

Preparation and characterization of Cf/Pollucite composites through geopolymer precursors

Continuous carbon-fibre-reinforced Cs-geopolymer composite (C_f/CsGP) were prepared, and its in-situ conversion was investigated during high-temperature treatments. The effect of treatment temperature on the thermal evolution process and mechanical properties of the resulting products were systematically evaluated. The results indicated that the crystallization temperature of C_f/CsGP composite was considerably delayed because the amorphous structure of carbon fibres was not conducive as a nucleation substrate for pollucite derived from the CsGP matrix. Moreover, the integrity of the corresponding resulting products derived from the C_f/CsGP composite were damaged due to thermal shrinkage that occurred during the high-temperature treatment process. When treatment temperature was ≤1200^oC, the mechanical properties of the corresponding products exhibited an upward trend, which was ascribed to the improvement of the densification degree of the resulting composite and well interface-bonding state between carbon fibres and pollucite. However, the mechanical properties of the resulting composites decreased with the treatment temperature continued increased from 1200 to 1400^oC. This phenomenon was attributed to the impairment of fibre properties caused by interfacial reactions.     

High-temperature adsorption of n-alkanes on ZSM-5 zeolites: influence of the Si/Al ratio and the synthesis method on the low-coverage adsorption properties

The influence of the composition and synthesis method on the low-coverage adsorption properties of C₅–C₉ n-alkanes on ZSM-5 zeolites was studied using the pulse chromatographic technique at temperatures between 200 and 400 °C. Experiments were performed with materials having Si/Al ratios between 12 and 400, synthesized with and without an organic template. For all ZSM-5 samples, the Henry adsorption constants increase exponentially with the carbon number, while zero-coverage adsorption enthalpies increase in a linear way. With decreasing Al content, the Henry constants and adsorption enthalpies decrease. An increase in adsorption enthalpy of 10.1 kJ/mol per added –CH₂– group is observed for an Si/Al ratio of 400, while an increase of 12.1 kJ/mol is found for an Si/Al ratio of 15. The contribution to the adsorption entropy per carbon atom depends on the ZSM-5 composition and varies between 11.2 and 14.4 J/(mol K). A significant effect of the synthesis method on the Henry constants, adsorption enthalpies and entropies is observed. All ZSM-5 samples synthesized using organic templates show the same unique relationship between adsorption enthalpy and entropy, different from that of zeolites synthesized without organic template.     

Influence of Si/Al ratio on the activity and durability of Pd-ZSM-5 catalysts for nitrogen oxide reduction by methane

The selective reduction of NO by methane on Pd-ZSM-5 catalysts with different Si/Al and Pd loadings was examined in the presence and absence of water vapor. At low Si/Al, NO reduction activity was high and stable, while at higher Si/Al, activity was lower and deactivation was significant. The deactivated samples showed PdO bands in the Raman spectra, which indicated that dispersed Pd cations play a key role in NO reduction. The influence of Si/Al on the stability of dispersed Pd cations suggested the importance of Al site pairs for the stable dispersion of Pd cations.     

Effects of graphite on the mechanical and microwave absorption properties of geopolymer based composites

In this paper graphite/metakaolin was first ball-milled to get homogeneous powder, which was then mixed with potassium silicate solution through mechanically stirring. Post curing, we got graphite/geopolymer composites with graphite to geopolymer ratio from 0 to 18 and part the samples were further dealt with heat treatment at 600 °C. Effects of the graphite content on the mechanical properties and microwave absorption properties of the composites were systematically investigated. The results proved that when graphite to geopolymer ratio is not higher than 12, graphite dispersed homogeneously in the composites. However, graphite agglomeration was noted when graphite to geopolymer ratios are 15 and 18. With the increase in graphite to geopolymer ratio, flexural strength and fracture toughness of the composites first increased, reaching the peak value and then decreased. When the graphite to geopolymer ratio is 12, the composite showed the highest flexural strength and fracture toughness, which should be explained by the mixing rule of composites since the mechanical properties of graphite are much higher than geopolymer matrix. With the increase in graphite content, the dielectric constants of the composite increased gradually, but the magnetic constants nearly kept unchanged. It implied that the main microwave absorbing mechanism would be dielectric loss of the composites. The maximum wave reflection loss showed similar trend to the mechanical properties of composites. It reached the peak value when graphite to geopolymer ratio is 12 and then started to decline, which might also be related to the graphite agglomeration. After 600 °C heat treatment, slight decline of the reflect loss peak and obvious decrease on the thickness corresponding to the maximum reflection loss were observed.     

ZSM-5分子筛形貌及硅铝比对甲缩醛气相羰基化反应性能的影响

通过调控合成方式、改变原料比例,制备纳米棒状、纳米球状、椭球状、圆柱状及棋子状等不同形貌及硅铝比的ZSM-5分子筛,并对其催化甲缩醛气相羰基化反应性能进行详细考察。在110℃、0.6 MPa、CO与甲缩醛流速分别为100 mL·min-1和0.035 mL·min-1条件下,硅铝物质的量比为30的棋子形ZSM-5分子筛表现出最佳的催化活性,甲缩醛转化率达31.9%,目标产物甲氧基乙酸甲脂选择性为21.4%。通过XRD、SEM、XRF、Py-FTIR、NH 3-TPD以及27 Al MAS NMR等对合成的分子筛进行详细表征,发现调控分子筛形貌及硅铝物质的量比可改变ZSM-5分子筛的酸性特征,并改变分子筛骨架中活性铝物种分布。适量的中强B酸酸位及分子筛交叉孔道内较高比例的活性铝物种分布可能是硅铝物质的量比30的棋子形ZSM-5分子筛表现出较好催化活性的原因。     

n(硅)∶n(铝)对HZSM-5分子筛膜催化裂解性能的影响

采用二次生长法在不锈钢管内壁上制备了不同n(硅)∶n(铝)的HZSM-5分子筛膜.采用XRD、SEM和原位吡啶吸附红外光谱对样品的结构和酸性质进行了表征,以超临界正十二烷的催化裂解为模型反应对样品的催化性能进行了评价.随着n(硅)∶n(铝)的增加,HZSM-5交织生长程度变大并且Brφnsted酸量逐渐减少.低n(硅)∶n(铝)的分子筛膜表面具有较高的Brφnsted酸量,在反应的初始阶段存在活性的快速下降行为.适当增加分子筛膜的n(硅)∶n(铝),可以减缓反应初始阶段的活性下降速度,从而明显提高HZSM-5分子筛膜的催化活性.但过高的n(硅)∶n(铝)使分子筛膜表面的酸量大幅减少、致密性增加,不利于裂解反应.n(硅)/n(铝)为125的HZSM-5分子筛膜具有最高的反应活性和初始活性稳定性.     

Selective catalytic reduction of NO with propene over CuMFI zeolites: dependence on Si/Al ratio and copper loading

Selective catalytic reduction of nitrogen oxide by propene in an oxidising atmosphere was studied on several CuMFI catalysts with different Si/Al ratios (11 Si/Al 100) and different copper loadings (between 0 and 5.5 wt.-%). From the results it was observed that the influence of zeolite Si/Al ratio on CuMFI catalytic activity for NO SCR by propene is dependent on the catalyst copper loading. Furthermore, the effect of catalyst copper loading on catalytic performance depended on the catalyst Si/Al ratio. The results also demonstrated that CuMFI catalysts with different Si/Al ratios and copper loadings, but with the same Cu/Al ratio and, therefore, the same copper exchange level have similar catalytic activity profiles for NO SCR.

It was further observed that not all Cu cations exchanged into MFI catalysts have equivalent catalytic activity for NO SCR, which made the existence of different copper environments on CuMFI catalysts evident, isolated Cu²⁺ ions being the most active species for NO SCR by propene.

Moreover, the results showed an improvement of the CuMFI catalytic activity at low temperatures by increasing the catalyst copper exchange level and, consequently, decreasing the number of Brönsted acid sites, which can be performed either by increasing the zeolite Si/Al ratio or copper loading.     

氧化物组分摩尔比对偏高岭土基地聚合物力学性能及结构的影响

以偏高岭土、水玻璃和氢氧化钠为主要原料制备地聚合物,研究了氧化物组分摩尔比(n(SiO_2)/n(Al_2O_3)、n(Na2O)/n(Al_2O_3)和n(H2O)/n(Al_2O_3))对偏高岭土基地聚合物抗压强度的影响,采用X射线衍射(XRD)和傅里叶变换红外光谱(FTIR)对地聚合物的结构和组成进行了分析。结果表明,三种摩尔比在一定范围内均存在最佳值,在最佳配比下制得的地聚合物样品3,7,28 d抗压强度分别为62.6,69.4,77.2 MPa。在地聚合反应中,主要形成无定形凝胶结构,当n(SiO_2)/n(Al_2O_3)3.6和n(Na2O)/n(Al_2O_3)0.8时,产生结晶度良好的沸石晶体。     

氧化物组分摩尔比对偏高岭土基地聚合物力学性能及结构的影响

以偏高岭土、水玻璃和氢氧化钠为主要原料制备地聚合物,研究了氧化物组分摩尔比(n(SiO_2)/n(Al_2O_3)、n(Na2O)/n(Al_2O_3)和n(H2O)/n(Al_2O_3))对偏高岭土基地聚合物抗压强度的影响,采用X射线衍射(XRD)和傅里叶变换红外光谱(FTIR)对地聚合物的结构和组成进行了分析。结果表明,三种摩尔比在一定范围内均存在最佳值,在最佳配比下制得的地聚合物样品3,7,28 d抗压强度分别为62.6,69.4,77.2 MPa。在地聚合反应中,主要形成无定形凝胶结构,当n(SiO_2)/n(Al_2O_3)<3.6和n(Na2O)/n(Al_2O_3)<0.8时,产生结晶度良好的沸石晶体。     

In situ processing of MWCNTs/leucite composites through geopolymer precursor

A serial of multi-walled carbon nanotubes (MWCNTs) reinforced geopolymer composites were prepared, and then heated at elevated temperature to fabricate MWCNTs/leucite composites by in situ transformation. Effects of high-temperature treatment on the microstructure evolution and mechanical performance of the composites were investigated. The results indicated that the introduction of MWCNTs could improve the mechanical properties of geopolymer, and the optimum content was 3 wt%. The mechanical performance declined instead with the further increase in MWCNTs content up to 5 wt%, which could be attributed to the agglomeration of MWCNTs. Significant improvements in mechanical properties were achieved after the composites were treated in a temperature range from 950 °C to 1200 °C relative to their original state before heat treatment. The significant improvements could be described to the matrix densification, and leucite formation as well as the proper interface bonding state between carbon nanotube and leucite matrix.     

Reaction kinetics and mechanical properties of a mineral-micropowder/metakaolin-based geopolymer

In this study, metakaolin was partially replaced with mineral micropowder to prepare a mineral-micropowder/metakaolin-based geopolymer was prepared under alkali activation, and the compressive and flexural strengths of various geopolymer specimens were determined. Geopolymer reaction kinetics were examined using the Johnson-Mehl-Avrami-Kolmogrov model, and the effects of the mineral-micropowder content on the properties and structure of the metakaolin-based geopolymer were investigated. Results revealed that micropowder addition significantly influenced the mechanical properties, microstructure, and reaction heat of the geopolymer. At a powder content of 30 wt%, the polymer exhibited superior mechanical properties; furthermore, the compressive and flexural strengths of the specimens cured for 28 d were 58.3 MPa and 12.6 MPa, which were 24.1% and 40% higher than those of the control group, respectively. Meanwhile, the geopolymer setting time was significantly reduced because the presence of calcium in mineral micropowder promoted the geopolymerisation reaction. Therefore, the formation of a multi-gel phase considerably enhanced the geopolymer structure.     

Modified supercritical CO2 extraction of amine template from hexagonal mesoporous silica (HMS) materials: Effects of template identity and matrix Al/Si molar ratio

In this work, the primary amine template has been extracted from freshly synthesized hexagonal mesoporous silica (HMS) materials by means of modified supercritical carbon dioxide at 60–85 °C under 10.0–20.0 MPa. The influences of amine identity and matrix Al/Si ratio on the extraction efficiencies and structural properties of HMS thus obtained are investigated in detail. The results show that the extraction efficiency is strongly dependent on the pore size of the HMS materials produced by five different templates. For aluminium-incorporated samples, the extraction efficiency is observed to decrease with the Al/Si molar ratio since as the Al/Si molar ratio increases, more amine will get protonated and the matrix/template interactions become stronger, subsequently rendering the extraction more difficult and the efficiency decrease. The formic acid modifier has resulted in better extraction performance than methanol, yielding higher extraction efficiencies. The SFE-treated materials exhibit better structural properties like higher pore volume and specific surface area as compared to those prepared by conventional calcinations. Besides, results of pyridine adsorption and conversion of 2-propanol to propylene suggest that the SFE-treated HMS materials may have higher acidity than the directly calcined samples.     

不同硅铝比HZSM-5分子筛对合成气一步法制二甲醚的影响

采用固定床高压反应装置,以工业用（CuO／ZnO／Al2O3）作为甲醇合成催化剂,四种不同硅铝比（硅铝比为25、38、50和150）的HZSM-5作为甲醇脱水催化剂,二者机械混合制备出一步法合成二甲醚双功能催化剂。考察了催化剂中脱水组分（HZSM-5分子筛）的硅铝比对二甲醚合成反应的影响,并通过BET、XRD和NH,-TPD等手段对催化剂进行表征。结果表明,一步法合成二甲醚催化剂中脱水组分HZSM-5的最佳的硅铝比为50。     

Al/Si比对SiO2-Al2O3-MgO系玻璃结构和性能的影响

SiO2-Al2O3-MgO系玻璃因具备强度大、弹性模量高等优异性能而用作高模量玻璃纤维的制备.采用熔融冷却法制备了不同Al/Si比的SiO2-Al2O3-MgO系基础玻璃,并研究了玻璃的结构和性能.红外光谱分析表明,玻璃网络结构由铝氧四面体[AlO4]和硅氧四面体[SiO4]相互连接而成.随着Al/Si比的增加,[AlO4]含量保持不变,[AlO6]含量逐渐增加.DSC分析表明,本系统玻璃的玻璃转变点Tg、成核温度Tx均随Al/Si比的增大而提高,玻璃的析晶倾向变强烈.热膨胀分析表明玻璃的热膨胀系数随Al/Si比的增大呈现先增大后减小的趋势.物理及机械性能测试结果如下:随Al/Si比的增大,密度、弹性模量均随之不断增大;而弯曲强度和维氏硬度则是持续降低.     

原位合成Cu-SSZ-13催化剂:硅铝比对NH_3-SCR催化性能的影响

通过一步法原位合成Cu-SSZ-13催化剂,评价不同硅铝比对其NH_3-SCR催化性能的影响,通过H_2-TPR、XRD和Rietveld精修表征催化剂。结果表明,不同硅铝比影响SSZ-13分子筛中活性Cu物种含量和分布。硅铝物质的量比为10时得到的Cu-SSZ-13催化剂具有优异的NH_3-SCR反应活性和稳定性,活性温度窗口最宽。