Investigations on the Synthesis of Zeolite ZSM-5 (III)

The effect of the chemical composition of the reacting mixture (RM) on the amount of zeolite ZSM-5 and other crystalline phases and the amorphous phase as well in the obtained preparations was investigated. Ethylenediamine (ED) served as a templating agent. The quantitative estimation of the phase composition was made on the ground of X-ray diffraction measurements. Zeolite ZSM-5 of maximum phase purity of 96%, contaminated mainly with quartz and mordenite, was obtained.     

The investigations on the synthesis of zeolite ZSM-5 (II)

Physical parameters, i.e. the effect of temperature and time of crystallization on the content of zeolite ZSM-5 in the obtained preparations were investigated. Two standard reacting mixtures were tested. The mixture of ethanol and ammonia was used as a templating agent. The phase composition of the preparations was determined on the ground of the X-ray diffraction method.     

以粉煤灰为原料采用两步法制备高纯度ZSM-5型沸石的研究

采用经碱熔融-离心提取处理后的粉煤灰为原料,经水热反应研究两步法合成高纯度ZSM-5型沸石的过程,探讨了碱灰比、焙烧温度对硅铝溶出量的影响,研究了碱度、晶化时间、晶化温度与硅铝比对合成ZSM-5型沸石的影响.结果表明:碱灰比为2.3∶1,焙烧温度为680 ℃时可获得最高的硅铝溶出量;当SiO2/Na2O =7(摩尔比),SiO2/Al2O3=45(摩尔比),晶化时间为68 h,晶化温度为180 ℃时可获得高纯度的ZSM-5型沸石.     

微波对Cu-ZSM-5催化剂结构及低温NH3-SCR脱硝活性的影响

以等体积浸渍法为基础,实验探究了不同干燥方法,微波干燥和普通干燥制得负载型铜基分子筛催化剂M-4Cu-ZSM-5和4Cu-ZSM-5的脱硝活性.通过XRD和氮气吸脱附表征手段,探究了不同干燥方法对催化剂孔道结构、物相结构及脱硝活性的影响.结果表明:铜的引入对分子筛的脱硝活性具有明显的提升作用;微波干燥的M-4Cu-ZSM-5催化剂在低于200 ℃时其催化脱硝活性略高于普通干燥的4Cu-ZSM-5催化剂,在200~300 ℃时4Cu-ZSM-5展现出更高的脱硝效率;微波处理会直接影响材料的孔道结构及活性物质的晶粒大小和分布,从而在一定程度造成催化活性的差异.     

Synthesis and characterization of ZSM-8-type zeolite crystals

Procedure for hydrothermal synthesis of ZSM-8-type zeolite crystals, using TEA—OH as a template, in the system having molar composition 16.2 (Na₂O) — Al₂O₃ — 117 (SiO₂) — 4.8 (TEA)₂O — 3887 H₂O at 170 °C is described. Results of characterization of these crystals by XRD, IR, EDAX, SEM, TGA, and adsorption studies are described and discussed. X-ray diffraction studies establish that the crystals are ZSM-8-type with structure similar to that of ZSM-5-type crystals. Crystals have prismatic bipyramidal morphology with average size 18–25 microns. Degased calcined samples adsorb xylenes in the order p > m > 0. Pore length per unit cell, estimated from n-hexane adsorption studies, is 46 Å.     

Synthesis Conditions of ZSM-5-Type Zeolites

Various experiments of the synthesis of chromium-containing ZSM-5-type zeolites were carried out in correspondence to a cubus in the space of the variables of synthesis. By means of correlation coefficients, F-values, stepwise multiple linear regression and cluster analysis the dependence of goal/characterization parameters on the synthesis variables were investigated. The computations show plausible explanations of the experimental results and gave additional hints which combinations of properties of the ZSM-5-type zeolite should be possible to design in the investigated space of synthesis conditions.     

酸碱改性ZSM-5分子筛及其噻吩烷基化性能的研究

首先采用碱处理HZSM-5分子筛,然后采用不同浓度的柠檬酸酸洗碱处理后的HZSM-5分子筛,制备具有微孔-介孔多级孔HZSM-5分子筛.通过XRD、SEM、BET和NH3-TPD等表征手段对处理后催化剂进行表征,考察了碱处理后酸洗对HZSM-5分子筛孔结构性质的影响,结果表明:适当浓度的柠檬酸酸洗碱处理后的ZSM-5分子筛,能够清除掉残留在分子筛孔道内的杂质,增大了分子筛的孔径;在小型固定床反应器上,研究了改性前后分子筛的噻吩烷基化反应活性和稳定性,结果表明:碱处理后采用适当浓度的柠檬酸酸洗后,催化剂的初活性虽然低于碱改性的分子筛,但稳定性较好,更适合噻吩烷基化反应.     

Influence of raw materials and potassium and silicon concentrations on the formation of a zeolite phase in a geopolymer network during thermal treatment

The development of porous materials based on geopolymers allows the benefits of eco-consumption, good insulating properties and good mechanical properties to be combined. For geopolymers to be useful, the development of an understanding of their properties under various conditions is important. Attention was given to the structural evolution of porous materials with heating. The structural evolutions were investigated using thermal analysis and infrared spectroscopy. The formation of a crystalline phase was observed and identified as a zeolite. To elucidate the roles played by the raw materials, silicon concentration and potassium concentration on the formation of the crystalline phase, three parameters in the foam synthesis process were modified. The influence of silica fume and metakaolin on the appearance of the crystalline phase was examined through the reactivity of the raw materials in contact with a potassium solution. Different behaviors directly linked to the network composition were observed. Silica-fume-based samples showed phase crystallization and dehydroxylation due to the large concentration of silicon, which likely led to the formation of hydrated silica species. The formation of the zeolite-phase network upon the application of heat depended only on the silica dissolution and was linked to the composition of silica in terms of the silicon species and grain size. Studying the crystalline phase formation by variation of the amount of potassium allowed the determination of a maximum silicon concentration and a minimum potassium concentration. The formation of the zeolite phase occurred at a potassium concentration greater than 3.5 mol·L^? 1 and a silicon concentration lower than 16.5 mol·L^? 1, which confirmed the presence of F-zeolites.     

Synthesis of nanosized ZSM‐5 using different alumina sources

Alumina sources can influence different aspects of ZSM‐5 crystallization and it leads to change in the properties of the final product. The crystallinity of nanosized ZSM‐5 zeolite from precursors mixtures containing different alumina sources, e.g. sodium aluminate, aluminum sulphate, aluminum hydroxide and alumina has been studied. The produced samples were investigated using XRD, SEM, FT‐ IR and BET surface area. The product obtained by sodium aluminate and aluminum sulphate was ZSM‐5 phase. Whereas, the product obtained by aluminum hydroxide and alumina was the albit phase. As‐synthesized ZSM‐5 was prepared by sodium aluminate, as alumina source was the highest crystallinity. It was found that the average crystallite size increased in the following order; alumina <aluminum hydroxide < aluminum sulphate < sodium aluminate. The surface area increased in the following order; aluminum sulphate < sodium aluminate < aluminum hydroxide < alumina due to increasing in crystallinity percentage of ZSM‐5. (© 2006 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Some observations on forms of NaA and NaX zeolites growing in the presence of triethanolamine

Using modified preparation conditions for silicate and aluminate solutions some differences in the result of large A- and X-type zeolites crystallization utilizing Charnell's procedure have been obtained. A-type zeolite crystals show clearly {110} faces. X-type zeolite occurs in mixed phase together with A-type zeolite as separate as well as overgrown crystals. These observations can be explained by structure defects in A-type crystals and by presence of polysilicate or/and too high aluminium content in the gel.     

Crystallization Kinetics of Silicalite-1: Use of Tetrapropylammonium Bromide and Chloride as Templates

Silicalite-1, the aluminum-free end number of the ZSM-5 zeolites, was synthesized from a batch composition of 3.25 Na₂O · 40.0 SiO₂ · 552 H₂O · 2.00 TPA by using tetrapropylammonium bromide (TPA-Br) or chloride (TPA-Cl) as templates in the temperature range of 100 to 175 °C in a batch system. Conversion of silica in the starting batch composition into silicalite-1 in the product was followed quantitatively. The activation energies of nucleation and crystallization were determined as 37.2 and 66.5 kJ/mol, respectively. The use of TPA-Cl as the template instead of TPA-Br results in longer induction period for crystallization to start and a larger crystal size in product.     

Influence of starting zeolite on synthesis of RUT type zeolite by interzeolite conversion method

In this study, hydrothermal conversions of ?BEA and FAU type zeolites using various structure-directing agents were carried out. Highly crystalline and pure RUT type zeolites were obtained from both zeolites in the presence of tetramethylammonium hydroxide. There were no major differences between the characteristics of the RUT type zeolites obtained from the two starting zeolites. However, the Si/Al ratio and the crystallization rate of the RUT type zeolites were strongly dependent on both the framework structure and the Si/Al ratio of the starting zeolite. That is, the crystallization rate of the RUT type zeolite from the *BEA type zeolite did not depend on the Si/Al ratio of the starting *BEA type zeolite, whereas the crystallization rate of the RUT type zeolite from the FAU type zeolite was dependent on the Si/Al ratio of the starting FAU type zeolite. This suggests that the chemical structure and the concentration of locally ordered aluminosilicate species produced by the decomposition/dissolution of the starting zeolite can be altered by changing the framework structure of the zeolite.     

非线性光学晶体δ-LiZnPO4的制备、结构及光学性能

研究了LiF为助熔剂体系下的δ-LiZnPO4的结晶特性,通过自发结晶得到了尺寸为1~3 mm的透明块状δ-LiZnPO4和Li4Zn(PO4)2共晶体,通过PXRD衍射分析和元素分析确定了共晶体的相组成,并对从共晶体中分离出的δ-LiZnPO4晶体结构进行了分析.结果表明:δ-LiZnPO4晶体具有非中心对称结构,属于正交晶系,空间群为Pna21,晶格常数a=1.00085 nm,b=0.49390 nm,c=0.66545 nm,Z=4;δ-LiZnPO4是由PO4、ZnO4和LiO4四面体构筑成的具有类似ABW型分子筛结构的化合物.采用水热法制备了尺寸约为10 μm的纯相透明的δ-LiZnPO4晶体.粉末倍频测试表明,δ-LiZnPO4晶体倍频效应约为KDP的1.7倍,紫外截止边约为218 nm,是一种有潜在应用价值的紫外非线性光学晶体.     

Formation of a Special Intermediate during Phase Transformation of Zeolite NaA to Nepheline

In the process of phase transformation of zeolite NaA to nepheline under hydrothermal conditions a special intermediate occurs. This is due to the high reaction rate of nepheline formation in the presence of water molecules. Consequently, the usually observed amorphous material with high condensed silica does not occur as separate phase. – The intermediate which is formed due to the destruction of the long-range order of zeolite is significantly short-range ordered. The phase transformation process starts at the outer surface of zeolite crystals, thus generating a diffusion barrier for sorption uptake processes.     

The influence of water steam on the direct phase transformation of zeolite NaA to nepheline by thermal treatment

Heating of zeolite NaA leads to the consecutive formation of amorphous phase, carnegieite and nepheline in the high temperature region. These phase transformations are influenced not only by temperature but also by the presence of water (inside of the crystals). Water causes destruction of zeolite framework by hydrolytic splitting of Si-O-Al-bonds in addition to thermal effects. Thus, the amorphous phase as the first product of phase transformation occurs in the presence of water steam at a lower temperature. The formation of the crystalline phases carnegieite and nepheline was observed in a temperature range, 300 K lower than usually, and without occurrence of the amorphous phase.     

固相法合成NaA型粉煤灰沸石对染料废水的吸附性能研究

以粉煤灰为原料,采用固相法合成NaA型粉煤灰沸石.通过静态吸附实验,研究了吸附时间、pH值、溶液浓度以及吸附温度对粉煤灰沸石吸附脱除亚甲蓝性能的影响.通过SME、XRD对产品进行表征,探讨了亚甲蓝在粉煤灰沸石上的吸附行为.结果表明:经XRD分析,合成产物主要为NaA型沸石.SEM分析表明,产物分别具有纺锤体及NaA型沸石立方体骨架结构;在吸附温度25 ℃,pH值>5,粉煤灰沸石投加量8 g·L-1,吸附30 min时,NaA型沸石对初始浓度为50~100 mg·L-1的亚甲蓝去除率均可达90;以上,较粉煤灰提高了45;;与商品沸石的吸附性能相当.合成的粉煤灰沸石吸附亚甲蓝过程符合Langmuir模型,其为单分子层吸附.     

Crystallization field study for the formation of single phase sodium clinoptilolite: Batch composition,seed and temperature effects

Although clinoptilolite is the most abundant zeolite mineral in nature, its synthesis under laboratory conditions has been difficult. A partial crystallization field study was done for the synthesis of clinoptilolite based on a nominal batch composition of 2.1Na₂O:Al₂O₃:10Si₂O:110H₂O to delineate the limits of composition and temperature within which sodium clinoptilolite can be produced as a single phase in high yields. Effects of temperature, SiO₂/Al₂O₃ molar ratio in the batch composition, and the use of different raw materials in batch preparation were studied. The need for the use of seed crystals for reproducible synthesis of clinoptilolite was established. (© 2009 WILEY‐VCH Verlag GmbH & Co. KGaA, Weinheim)     

Tetrabutylphosphonium Cation as Template in the Kinetics of Crystallisation of ZSM-5

Zeolite ZSM-5 was synthesised using ethyl silicate ester 40 and sodium aluminate so as to get the gel mix with SiO₄/Al₂O₃ = 90 employing TBPCl and TPABr templates separately (for comparison) at temperatures 423 K, 448 K, and 473 K. Nucleation and crystallisation processes were kinetically analysed. Activation energies for nucelation and crystallisation and the geometric factors have been evaluated. Correlations were found between the kinetic characteristics and the habits of the crystals formed. The study of the composition and morphology of the intermediates, with the support of SEM pictures, reveal the different mechanisms operating in the templating action of TBPCl and TPABr molecules.     

The properties of hydrogen forms of zeolite T obtained by the treatment with hydrochloric acid at 22°C

Hydrogen forms of zeolite T obtained by the treatment of synthetic zeolite of erionite-offretite type with hydrochloric acid at 22°C were tested with the methods of chemical analysis, sorption and X-ray diffraction. The influence of the variations in the number of treatments with acid, the concentration of acid and the calcination at 500°C on the properties of the samples was observed. It was found that the modification runs in two steps. The existence of the threshold of stability of the zeolite T structure under the treatment with 0.1 N HCl was indicated at the degree of decationization of 45–48% and the degree of dealumination of 25–28%. It was also found that about 30–33% of alkali cations in zeolite T are at the more accessible positions.     

放电等离子烧结制备Ba2+掺杂γ-La2S3陶瓷及其性能研究

以气固反应硫化制备的γ-La2S3粉体为原料,采用放电等离子烧结(SPS)技术制备出γ-La2S3多晶陶瓷.研究了Ba2+掺杂量对得到γ-La2S3粉体物相结构的影响,并分析了烧结温度、再硫化工艺参数对γ-La2S3多晶陶瓷微观组织结构和红外透过率的影响.结果表明:掺入Ba2有利于低温获得稳定的高温型γ-La2S3相,在nLa/nBa为5 ～15时能够得到纯相的γ-La2S3粉体.在烧结温度为1150℃,保温时间为5min时制备出的γ-La2S3陶瓷致密,无明显气孔,在CS2气氛下再硫化2.5h后,在10 ～ 14μm波段的红外峰值透过率达到42％.