表面润湿法合成β沸石体系中晶种作用的研究

系统研究了表面润湿法合成β沸石的体系中,干晶种、润湿态晶种、异晶晶种(Y沸石、ZSM 5沸石)以及碱处理β沸石晶种在此晶化体系中的作用.采用β沸石产品及异晶作晶种时,可使产品的相对结晶度稍有提高,但对沸石微晶核的结构导向作用不明显.经浓碱液处理20min后的β沸石产品(碱处理晶种)作晶种引入晶化体系后,可以显著提高产品的相对结晶度,降低模板剂的用量,缩短晶化诱导期,成为表面润湿法合成β沸石体系的有效晶种形式.     

Synthesis, characterization, and ion-exchange properties of colloidal zeolite nanocrystals

Here, we present physical–chemical properties of Linde type A (LTA) zeolite crystals synthesized via conventional hydrothermal and microwave heating methods. Both heating methods produced LTA crystals that were sub-micron in size, highly negatively charged, super-hydrophilic, and stable when dispersed in water. However, microwave heating produced relatively narrow crystal size distributions, required much shorter heating times, and did not significantly change composition, crystallinity, or surface chemistry. Moreover, microwave heating allowed systematic variation of crystal size by varying heating temperature and time during the crystallization reaction, thus producing a continuous gradient of crystal sizes ranging from about 90 to 300 nm. In ion-exchange studies, colloidal zeolites exhibited excellent sorption kinetics and capacity for divalent metal ions, suggesting their potential for use in water softening, scale inhibition, and scavenging of toxic metal ions from water.     

Conversion of silica by-product into zeolites by thermo-sonochemical treatment

The fine powdered silica by-product of processing of aluminum fluoride (fertilizer plant, Lithuania) was used for zeolite synthesis as silica and aluminum source. The effect of sonication time and the time of hydrothermal synthesis on crystallinity of the synthesized zeolite were studied. This allowed the transformation of the by-product to the mixture of Na–P zeolite and Na–X zeolite. It was determined that ultrasonic-assisted hydrothermal action effected the “diamond” shape formation of Na–P zeolite with clear crystal edges. Na–P zeolite had the morphology of pseudo-spherical forms constituted by small plates when hydrothermal treatment (without sonication) was use for the preparation of zeolites. Moreover, it was determined that ultrasonic-assisted hydrothermal method effected a reduction in the crystal size compared with the zeolites which were synthesized only by using hydrothermal synthesis. The total amount of zeolites as high as 88–93% was achieved after 24 h of hydrothermal treatment followed or unfollowed by sonication. By using longer duration (20 min) of ultrasound pretreatment it is possible to reduce the duration of hydrothermal synthesis: from 24 h to 12 h of hydrothermal treatment. In this case, similar results of total amount of zeolites were detected. In the present work, low-cost raw materials, such as silica by-product have been investigated for the production of zeolites.     

(K,Mo)Y分子筛中钼组分的EXAFS研究

应用同步辐射Eextended X-ray Ab sorption Fine S tructure(EXAFS)技术研究固态法制备的KHMoY分子筛的氧化态和硫化态样品以及硫化态KHY／MoO3样品中钼组分的局域配位环境结构,并与KHMoY和KHY／MoO3 样品催化加氢活性结果进行对照。结果表明,随原子比（K＋2Mo）／Al的变化,钼原子周围的配位环境有显著的差异。当（K＋2Mo）／Al时,KHMoY和KHY/MoO3硫化后,钼组分主要以MoS2小原子簇分散在分子筛超笼中;（K＋2Mo)/Al>1时,钼组分则有两种存在环境,即分子筛超笼中的和分子筛外表的钼组分。分子筛超笼中的Mo S2原子簇的催化加氢合成醇选择性较高;分子筛外表面的MoS2微小颗粒的尺寸相对于超笼中的要大许多,其合成醇选择 性较低。     

Zn-Y/BEA上乙醇一步法制1，}3-丁二烯的反应机理及优异催化剂筛选

随着beta分子筛负载双金属催化剂的开发,乙醇一步法制1,3-丁二烯}取得了突破性进展. 然而,从乙醇到丁二烯的反应机理复杂,尚未完全阐明,也缺乏基于中心金属原子的催化剂筛选. 本文采用密度泛函理论计算方法,系统地研究了乙醇在Zn-Y/BEA催化剂上一步法制丁二烯的机理. 结果表明,乙醇脱氢更倾向于在Zn位点进行,决速步骤的反应热仅为0.77 eV;羟醇缩合生成丁二烯更倾向于在Y位点进行,决速步骤的反应热仅为0.69 eV. 基于所揭示的反应机理,选择了六种元素代替Y来筛选用于该反应的Zn-M/BEA(M=Sn、Nb、Ta、Hf、Zr、Ti)的优良组合. 结果表明,与其他六种催化剂相比,Zn-Y/BEA仍是最优选的催化剂,Zn-Zr/BEA、Zn-Ti/BEA和 Zn-Sn/BEA也是乙醇转化为丁二烯的可行催化剂. 本工作不仅揭示了Zn-Y/BEA催化乙醇一步法制丁二烯的反应机理,而且为该反应提供了其他可能的催化剂选择.     

Ultrasound-assisted rapid hydrothermal design of efficient nanostructured MFI-Type aluminosilicate catalyst for methanol to propylene reaction

The influence of ultrasound-assisted rapid hydrothermal synthesis of aluminosilicate ZSM-5 catalysts was examined in this work. A series of MFI-type nanostructured materials with sonochemical approach and conventional heating were synthesized and evaluated for conversion of methanol to propylene reaction. The prepared samples were tested by characterization analyses such as XRD, FESEM, BET-BJH, FTIR, TPD-NH₃ and TG/DTG. The obtained results confirmed that ultrasound treatment enhanced the nucleation process and crystal growth for ZSM-5 sample synthesized at moderate temperature of 250 °C. Therefore, it was found the formation of pure MFI zeolite with high crystallinity and improved textural, structural and acidic properties for ZSM-5(UH-250) sample compared with the other zeolites. This observation was attributed to the relationship between the perfect crystallization mechanism and catalytic properties, which led to producing an efficient MFI zeolite toward the optimal catalytic performance. In this manner, the methanol conversion and products selectivity of prepared materials were carried out in MTP reaction at 460 °C and atmospheric pressure. The ZSM-5(UH-250) zeolite with slower deactivation regime exhibited the constant level of methanol conversion (84%) and high propylene selectivity (78%) after 2100 min time on stream. Moreover, the synthesis pathway for MFI zeolite at moderate temperature and also deactivation mechanism of improved sample were proposed.     

Sonochemically prepared hierarchical MFI-type zeolites as active catalysts for catalytic ethanol dehydration

In this paper, the ultrasonic-assisted desilication technique was reported as an attractive and efficient way for the preparation of hierarchical zeolites with MFI structure type. The prepared materials were used as active catalysts for the dehydration of ethanol into diethyl ether and ethylene. For all catalysts, the selectivity to diethyl ether was ca 95% or higher up to 210 °C, with catalytic activity in the range of 40–68%. In case of desilicated zeolites, at 270–290 °C, the conversion of ethanol was full with selectivity to ethylene ca 80%. MFI-type commercial zeolite was treated with a sodium and/or tetrabutylammonium hydroxide aqueous solutions (NaOH or NaOH/TBAOH) for 30 min. In the case of the application of ultrasounds, a QSonica Q700 sonicator (60 W and 20 kHz) equipped with a “1” diameter horn was used. In all cases, desilication was performed in an ice bath in order to keep the procedure conditions at low temperature.It was indicated that the use of ultrasounds during desilication procedure caused higher extraction of silicon and aluminum, which was connected with an elevated mesoporosity in relation to the samples modified in the absence of ultrasounds. Ultrasonic-assisted treatment of MFI-type zeolite caused also an apparent formation of numerous holes inside zeolite grains, resembling the look of “swiss cheese”. Furthermore, it was indicated that the samples prepared using ultrasonic irradiation exhibited enhanced catalytic properties in the dehydration of ethanol. For instance, MFI-type zeolite treated with NaOH/TBAOH alkaline mixture containing 10 mol% of TBAOH in the presence of ultrasounds (M−10 s) demonstrated higher both conversion of ethanol (59% vs. 47%) and selectivity to diethyl ether (95% vs. 93%) in comparison with zeolite modified conventionally (M−10c).The best catalyst was zeolite ultrasonically desilicated with NaOH/TBAOH solution of 70 mol% of TBAOH (M-70s). Generally, this catalyst indicated the highest conversion of ethanol, very high selectivity to diethyl ether (94-100%) at 150-210  °C and the highest selectivity to ethylene among investigated catalysts (21%, 66% and 84%) at 230  °C, 250 ^oC and 270  °C.     

Synthesis of Pt modified ZSM-5 and beta zeolite catalysts: influence of ultrasonic irradiation and preparation methods on physico-chemical and catalytic properties in pentane isomerization

Influence of preparation methods and ultrasound irradiation on physico-chemical and catalytic properties was investigated by synthesizing Pt-ZSM-5 and Pt-Beta catalysts by in-situ and impregnation methods and applying ultrasound irradiation to synthesis gel mixture of ZSM-5 and Beta zeolites. It was concluded from the X-ray powder diffraction patterns of Pt-ZSM-5 and Pt-Beta zeolite catalysts that introduction of Pt by in-situ method and ultrasound irradiation did not influence the structures of ZSM-5 and Beta zeolites. Morphology of ZSM-5 and Beta zeolites were investigated by scanning electron microscopy. SEM micrographs showed that the Pt-ZSM-5-IS-US catalyst synthesized by in-situ method with ultrasound irradiation resulted in smaller crystals of ZSM-5 than Pt-ZSM-5-IS catalyst prepared without ultrasound irradiation. Furthermore SEM micrographs of Pt-Beta-11-IS-US zeolite synthesized using ultrasound irradiation showed much smaller crystals than Pt-Beta-11-IM indicating that ultrasound irradiation had a significant effect on the morphology of Beta zeolite. Conversion of n-pentane and selectivity to iso-pentane over the Pt-ZSM-5-IS-US zeolite catalysts prepared by ultrasound irradiation during in-situ introduction of platinum was higher than the catalysts prepared without the ultrasound irradiation. Furthermore ultrasound irradiated and in-situ synthesized Pt-Beta-11-IS-US catalyst also showed higher selectivity to iso-pentane than Pt-H-Beta-11-IM prepared by impregnation method.     

Gas sensing performance of ion-exchanged Y zeolites as an impedimetric ammonia sensor

Zeolites are valuable chemical catalysts and excellent sorbents; several reports have used zeolites for chemical gas sensing. This article systematically investigates the gas sensing performance of ion-exchanged Y zeolites. The interactions between zeolites and ammonia can effectively improve their ionic conductivity, and the zeolites are explored as an impedimetric ammonia sensor. The sensor development was supported by a detailed interpretation of the ammonia-supported ionic conductivity, which was deduced from the measurements of temperature-programmed impedance over a wide temperature range and provides an understanding of the sensing parameters (e.g., temperature and concentration of ammonia). The elevated temperature accelerates the kinetics of the ammonia adsorption/desorption, but it reduces the adsorbing capacity of the zeolite. The thickness of the zeolite pellet is a key parameter for determining the detection limit. Ag-Y and H-Y have higher working temperatures than the alkali cation-exchanged Y zeolite. The excellent selectivity of Ag-Y and Na-Y indicates that they are good candidates as practical ammonia sensors.

     

Long-range diffusion in beds of nanoporous particles: pitfalls and potentials

Owing to the recent progress in the area of hardware and software of the pulsed field gradient NMR technique, molecular transport in real-life zeolite systems, such as zeolite beds and particles of formulated fluid catalytic cracking (FCC) catalysts, can be investigated in detail. These studies have revealed a number of important features of molecular transport in zeolites, which are reviewed in the present paper. In particular, the anomalous character of intracrystalline diffusion in MFI-type zeolites, dependence of the tortuosity factor in zeolite beds on diffusion regime and the role of various modes of diffusion in transport limitations arising for catalytic reactions in FCC catalysts will be discussed.     

Effects of ultrasonic treatment on zeolite NaA synthesized from by-product silica

The synthesis of zeolite NaA from silica by-product was carried out in the presence of 20 kHz ultrasound at room temperature. Zeolites obtained in this type of synthesis were compared to zeolites obtained by performing conventional static syntheses under similar conditions. The sonication effects on zeolite NaA synthesis were characterized by phase identification, crystallinity etc. The effects of different parameters such as crystallization time and initial materials preparation methods on the crystallinity and morphology of the synthesized zeolites were investigated. The final products were characterized by XRD and FT-IR. It was possible to obtain crystalline zeolite NaA from by-product silica in the presence of ultrasound.     

Synthesis of silica-pillared clay (SPC) with ordered mesoporous structure by one-step method without preswelling process

The simultaneous intercalation of surfactants and TEOS into clay interlayers and subsequent intragallery ammonia-catalyzed hydrolysis of TEOS resulted in mesoporous silica-pillared clay (SPC). These SPC materials exhibited refractions corresponding to a basal spacing of 3.7-4.3 nm, a uniform pore size of 2.5-3.16 nm and large surface areas of 567-576 m²/g. Our results indicate that surfactants play a decisive role in pore formation, because they act as micelle-like template during the hydrolysis of TOES. Moreover, the pore size of SPC derivatives is controllable by the molecular length of surfactant. All of the SPC materials reported here exhibit high catalytic activity and selectivity for coker gas oil (CGO) cracking reaction in comparison to parent MCM-41 and Al-MCM-41. The excellent acid catalytic activity, together with their sable, well-organized porous structure, opens up new opportunities for applications in catalysis.     

Synthesis of MCM-22 zeolite by an ultrasonic-assisted aging procedure

The synthesis of MCM-22 zeolite under hydrothermal crystallization conditions has been performed by an ultrasonic-assisted aging procedure. The ultrasonic-assisted aging of the initial aluminosilicate gel can shorten the crystallization time of MCM-22, decrease the amount of hexamethyleneimine (HMI) used, and broaden the range of SiO(2)/Al(2)O(3) ratios. By using the ultrasonic aging, pure phase of high-silica MCM-22 products with SiO(2)/Al(2)O(3)>100 can be obtained. When SiO(2)/Al(2)O(3) 相似文献   

Effects of water and combustibles on single crystal zeolite conductivity

The conductivity behavior of the natural single crystal zeolites ANA, BRE, CHA, HEU, PHI and STI was investigated in the temperature range between 60 °C and 110 °C. The effect of combustible gas components on the conductivity was also investigated using constant water vapor pressure conditions. In the temperature range studied, the conductivity is assumed to be mainly ionic and zeolitic water remains within the channel and cage system of the structures. All zeolites do have different frameworks, channel systems, channel sizes, channel cations and water contents. Dependent on the zeolite type, water partial pressures and combustible gas components cause different effects on the conductivity which are correlated with the geometry, charge distribution and occupation of the channels and cages of the respective zeolite single crystal. Paper presented at the 5th Euroconference on Solid State Ionics, Benalmádena, Spain, Sept. 13–20, 1998.     

Interaction between guest AgI and host zeolite FAU studied by optical spectra and EXAFS

AgI molecules were dilutely adsorbed into nano-cages of Na⁺, K⁺ and Cs⁺ type FAU zeolites in order to understand the interaction between host zeolite and guest AgI. This interaction was investigated using optical absorption spectroscopy and extended X-ray absorption fine structure (EXAFS). The optical spectra strongly depend on the type of the alkali cations. Compared with the lowest absorption band of AgI molecules in gas phase, the spectra of AgI molecules adsorbed in the zeolite cages shifts to higher energy in the order of Cs⁺, K⁺, and Na⁺. On the contrary, Ag-I bond lengths of adsorbed AgI molecules obtained from EXAFS were independent of the type of the alkali-cations. The bond length was very close to gas phase AgI molecules. Therefore, the interaction between AgI molecules and the zeolite, whose magnitude is Na⁺ > K⁺ > Cs⁺, is important in the photo-excited electronic state.     

Ultrasonic assisted synthesis of Bikitaite zeolite: A potential material for hydrogen storage application

Li containing Bikitaite zeolite has been synthesized by an ultrasound-assisted method and used as a potential material for hydrogen storage application. The Sonication energy was varied from 150 W to 250 W and irradiation time from 3 h to 6 h. The Bikitaite nanoparticles were characterized by X-ray diffraction (XRD), infrared (IR) spectral analysis, and field-emission scanning electron microscopy (FESEM) thermo-gravimetrical analysis and differential thermal analysis (TGA, DTA). XRD and IR results showed that phase pure, nano crystalline Bikitaite zeolites were started forming after 3 h irradiation and 72 h of aging with a sonication energy of 150 W and nano crystalline Bikitaite zeolite with prominent peaks were obtained after 6 h irradiation of 250 W sonic energy. The Brunauer–Emmett–Teller (BET) surface area of the powder by N₂ adsorption–desorption measurements was found to be 209 m²/g. The TEM micrograph and elemental analysis showed that desired atomic ratio of the zeolite was obtained after 6 h irradiation. For comparison, sonochemical method, followed by the hydrothermal method, with same initial sol composition was studied. The effect of ultrasonic energy and irradiation time showed that with increasing sonication energy, and sonication time phase formation was almost completed. The FESEM images revealed that 50 nm zeolite crystals were formed at room temperature. However, agglomerated particles having woollen ball like structure was obtained by sonochemical method followed by hydrothermal treatment at 100 °C for 24 h. The hydrogen adsorption capacity of Bikitaite zeolite with different Li content, has been investigated. Experimental results indicated that the hydrogen adsorption capacities were dominantly related to their surface areas as well as total pore volume of the zeolite. The hydrogen adsorption capacity of 143.2 c.c/g was obtained at 77 K and ambient pressure of (0.11 MPa) for the Bikitaite zeolite with 100% Li, which was higher than the reported values for other zeolites. To the best of our knowledge, there is no report on the synthesis of a Bikitaite zeolite by sonochemical method for H₂ storage.     

Synthesis of NaP zeolite at room temperature and short crystallization time by sonochemical method

NaP zeolite nano crystals were synthesized by sonochemical method at room temperature with crystallization time of 3 h. For comparison, to insure the effect of sonochemical method, the hydrothermal method at conventional synthesis condition, with same initial sol composition was studied. NaP zeolites are directly formed by ultrasonic treatment without the application of autogenous pressure and also hydrothermal treatment. The effect of ultrasonic energy and irradiation time showed that with increasing sonication energy, the crystallinity of the powders decreased but phase purity remain unchanged. The synthesized powders were characterized by XRD, IR, DTA TGA, FESEM, and TEM analysis. FESEM images revealed that 50 nm zeolite crystals were formed at room temperature by using sonochemical method. However, agglomerated particles having cactus/cabbage like structure was obtained by sonochemical method followed by hydrothermal treatment. In sonochemical process, formation of cavitation and the collapsing of bubbles produced huge energy which is sufficient for crystallization of zeolite compared to that supplied by hydrothermal process for conventional synthesis. With increasing irradiation energy and time, the crystallinity of the synthesized zeolite samples increased slightly.     

Effect of preparation and metal content on the introduction of Fe in BEA zeolite, studied by DR UV-vis, EPR and Mössbauer spectroscopy

Fe-containing SiBEA zeolites were prepared by a two-step postsynthesis method: creation of vacant T-sites by dealumination of tetraethylammonium BEA zeolite with nitric acid and then impregnation of the resulting SiBEA zeolite with an aqueous solution of Fe(NO₃)₃. X-ray diffraction shows that iron is incorporated in SiBEA at lattice sites. The presence of Fe in its oxidation state +3 and at isolated tetrahedral sites for low metal content, was demonstrated by diffuse reflectance UV-vis, EPR and Mössbauer spectroscopy. For high iron content, diffuse reflectance UV-vis and Mössbauer spectra revealed the additional presence of extra-lattice FeO_x oligomers and superparamagnetic Fe-oxyhydroxide. Mössbauer spectroscopy identified superparamagnetic Fe-oxyhydroxide as the main phase when basic conditions are used for the preparation.     

二氧化硅改性分子筛催化生物质基多元醇制备对二甲苯

本文证明了在二氧化硅改性的分子筛催化作用下,生物质基多元醇(如山梨醇、木糖醇、赤藓糖醇、甘油和乙二醇)可以经过催化裂解、烷基化和异构化等反应,生成高附加值的化学品(对二甲苯).与HZSM-5分子筛催化剂相比,二氧化硅改性的分子筛降低了分子筛催化剂的外表面酸和孔径,从而显著的提高对甲苯的选择性和产率.本文详细讨论了催化剂、甲醇添加剂、反应温度和不同类型多元醇原料对对二甲苯选择性和产率的影响.甲醇的添加促进多元醇催化裂解中的烷基化反应,提高了二甲苯的产率.在15%SiO_2/HZSM-5催化剂作用下,对二甲苯的产率最高可达到10.9 C-mol%,对二甲苯在二甲苯中选择性达到91.1%.本文通过研究相关重要反应和催化剂特性,揭示了生物质基多元醇催化裂解制备对二甲苯的反应路径.     

Experimental and numerical investigation of the effect of ultrasound on the growth kinetics of zeolite A

Ultrasound is a promising technology for the improvement of zeolite production, due to its beneficial effects on mass transfer and nucleation. However, a broad understanding of the sonication parameters that influence the growth of zeolites most is still lacking. In the present work, zeolite A was synthesized and the kinetic model of Gualtieri was used to obtain information about the crystallization parameters. The effect of the sonication power and duration on the relative crystallinity and particle size distribution were investigated using a Langevin-type transducer operating at 40 kHz. The experimental data shows that ultrasound has a significant effect on the nucleation and growth. With that, a reduction of up to 40 % of the initial synthesis time can be achieved. Additionally, a narrower particle size distribution is achieved when ultrasound is used during the zeolite A synthesis.