The structure-directing role of heterologous seeds in the synthesis of zeolite

Zeolites have been widely used as catalysts,ion-exchangers,and adsorbents in chemical industries,detergent industry,steel industry,glass industry,ceramic industry,medical and healthfield,and environmentalfield,and recently applied in energy storage.Seed-assisted synthesis is a very effective approach in promoting the crystallization of zeolites.In some cases,the target zeolite cannot be formed in the absence of seed zeolite.In homologous seed-assisted synthesis,the structure of the seed zeolite is the same to that of the target zeolite,while the structure of the seed zeolite is different to that of the target zeolite in the heterologous seed-assisted synthesis.In this review,we briefly summarized the heterologous seed-assisted syntheses of zeolites and analyzed the structure-directing effect of heterologous seeds and surveyed the“common composite building units(CBUs)hypothesis”and the“common secondary building units(SBUs)hypothesis”.However,both hypotheses cannot explain all observations on the heterologous seed-assisted syntheses.Finally,we proposed that the formation of the target zeolite does need nuclei with the structure of target zeolite and the formation of the nuclei of the target zeolite can be promoted by either the undissolved seed crystals with the same CBUs or SBUs to the target zeolite or by the facilitated appropriate distribution of the specific building units due to the presence of the heterologous seed that does not have any common CBUs and SBUs with the target zeolite.

OSDA-free synthesis of FeZSM-22 zeolite from natural minerals for n-octane hydroisomerization

A seed-directed approach to synthesizing Fe ZSM-22 zeolite without organic structure directing agent(OSDA)was developed by using Fe-rich diatomite as all aluminum and iron sources.The Fe ZSM-22zeolite with optimal crystallinity and purity can be obtained by systematically adjusting feed composition and synthesis conditions.Characterizations show that Fe ZSM-22 zeolite synthesized with OSDA-free owns high crystallinity,obvious thin needle-shaped morphology and high Bronsted/Lewis acid ratio.Significantly,when used for n-octane hydroisomerization reaction,its derived catalyst exhibits the best catalytic performance reflected by the highest selectivity to C_(8)isomers compared to the two reference catalysts prepared based on a Fe-containing and a Fe-free ZSM-22 synthesized through an OSDA-directed route from natural diatomite and conventional chemicals,respectively.This work provides an alternative route to sustainably synthesizing heteroatomic zeolites with high performance.

Facile synthesis of hierarchical NaX zeolite from natural kaolinite for efficient Knoevenagel condensation

Zeolite catalysts have found extensive applications in the synthesis of various fine chemicals.However,the micropores of zeolites impose diffusion limitations on bulky molecules,greatly reducing the catalytic efficiency.Herein,we explore an economic and environmentally friendly method for synthesizing hierarchical NaX zeolite that exhibits improved catalytic performance in the Knoevenagel condensation reaction for producing the useful fine chemical 2-cyano-3-phenylacrylate.The synthesis was achieved via a low-temperature activation of kaolinite and subsequent in-situ transformation strategy without any template or seed.Systematic characterizations reveal that the synthesized NaX zeolite has both intercrystalline and intra-crystalline mesopores,smaller crystal size,and larger external specific surface area compared to commercial NaX zeolite.Detailed mechanism investigations show that the inter-crystalline mesopores are generated by stacking smaller crystals formed from in-situ crystallization of the depolymerized kaolinite,and the intra-crystalline mesopores are inherited from the pores in the depolymerized kaolinite.This synthesis strategy provides an energy-saving and effective way to construct hierarchical zeolites,which may gain wide applications in fine chemical manufacturing.

Synthesis of mordenite by solvent-free method and its application in the dimethyl ether carbonylation reaction

Mordenite with different Si/Al ratios were synthesized by solvent-free method and used for dimethyl ether(DME)carbonylation reaction.The influence of Si/Al ratio in the feedstock on the structure,porosity and acid sites were systematically investigated.The characterization results showed that with the increase of Si/Al ratio in the feedstock,part of silicon species fail to enter the skeleton and the specific surface area and pore volume of the samples decreased.The amount of weak acid and medium strong acid decreased alongside with the increasing Si/Al ratio,and the amount of strong acid slightly increased.The Al atoms preferentially enter the strong acid sites in the 8 member ring(MR)channel during the crystallization process.The high Si/Al ratio sample had more acid sites located in the 8 MR channel,leading to more active sites for carbonylation reaction and higher catalytic performance.Appropriately increasing the Si/Al ratio was beneficial for the improvement of carbonylation reaction activity over the mordenite(MOR)catalyst.

Synthesis of Nanosized NaY Zeolite by Confined Space Method

Nanosized NaY crystals have been prepared from metakaolin and sodium silicate by confined space synthesis with starch additive. It is found that the product has a narrow crystal size distribution (50-100 nm), high Si/Al ratio (Si/Al=4.6-6.1), high surface area (1090 m2/g) and the average diameter of nanosized NaY (75 nm) synthesized is 30 nm, it is smaller than that of without starch additive.

Synthesis,characterization and catalytic properties of Y-β zeolite composites

Y-β zeolite composites were hydrotherrnally synthesized by using high silica Y zeolite as the precursor and characterized by XRD, N2 adsorption, SEM and IR spectra of pyridine. The result showed that the N2 adsorption-desorption isotherm of the zeolite composites had a distinct hysteresis loop, and the SEM result showed that the zeolite composites had a different morphology from Y, β and the corresponding physical zeolite mixture. The acid catalytic performance of the zeolite composite catalysts was investigated in the hydrocracking and hydroisomerization of n-octane, and the results showed that the composite materials exhibited an excellent hydrocracking activity and good hydroisomerization performance. The yield of i-C4 over the zeolite composite catalyst was 4.45% higher than that on the corresponding zeolite mixture in the n-octane hydrocracking process at 553 K. The isomerization ability of n-octane over the composite catalyst was 3.6 fold that of the corresponding mixture at 503 K.

In Situ Synthesis of NaY Zeolite with Coal-Based Kaolin

NaY zeolites were in-situ synthesized from coal-based kaolin via thehydrothermal method. The effects of various factors on the structure of the samples were extensivelyinvestigated. The samples were characterized by N_2 adsorption, XRD, IR and DTG-DTA methods, andthe results show that the crystallization temperature and amount of added water play an importantrole in the formation of the zeolite structure. The 4A and P zeolites are the competitive phasepresent in the resulting product. However, NaY zeolites with a higher relative crystallinity,excluding impure crystals and the well hydrothermal stability, can be synthesized from coal-basedkaolin. These zeolites possess a larger surface area and a narrow pore size distribution, and thismeans that optimization of this process might result in a commercial route to synthesize NaYzeolites from coal-based kaolin.

Secondary Synthesis of Ti-containing Zeolite

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Synthesis of Zeolite a from Natural Ca-Bentonite Using a Direct Alkali Hydrothermal Approach

Ca-bentonite can be converted into zeolites A through hydrothermal alkaline treatment by varying the synthetic parameters. This study focuses on the effect of initial Si/Al molar ratio, NaOH concentration on the type of formed zeolite A. The Ca-bentonite (China, Fuxin)were mixed with an aqueous NaOH solution, Al(OH)3 powder and hydrothermally treated at about 90 ℃,12 h. Different types of zeolites (zeolite X, P, and A),sodalite were synthesized after the treatment. Zeolites were characterized and quantified by means of XRD and SEM analysis. Zeolite A predominantly formed with 0.5≤Si/Al≤2.0 was produced and zeolite X, P formed with Si/Al>2.0 under the 2.2mol/LNaOH concentration; Sodalite was also formed under high NaOH molarities. Shape of zeolite A is show the cube by the SEM micrograph.

Synthesis, Characterization and Catalytic Properties of Zeolite [B, Al, Ga, Fe]-ZSM-5

Zeolite [B,Al, Ga, Fe]-ZSM-5, containing several heteroatoms, was synthesized for the first time under. hydrothermal conditions. Characterization of the sample using various techniques such as XRD, IR, ESR, TG-DTA, SEM and XRF indicates that the heteroatoms are located in the framework, similar to the situations of the heteroatoms present in the zeolites [B]-, [Al]-, [Ga]- and [Fe]-ZSM-5. The study of the catalytic properties for reactions of cracking and dehydrogenation of ethylbenzene reveals that the heteroatoms function independently and there are no mutual interactions between the heteroatoms.

Studies on the Synthesis, Properties and Preparation Methods of Zeolite ZK-4

A zeolite designated as ZK-4 was synthesized hydrothermally in the system (TMA)2ONa2O-Al2O3- SiO2- H2O at 80 - 100℃ with tetramethylammonium hydroxide as an organic templating agent. The pure zeolite ZK-4 could be prepared by using the mother liquor obtained after filtration as the source of templating agent. The effect of some synthetic conditions such as the amount of tetramethylammonium hydroxide used, n [ (TMA)2O + Na2O] /n (Al2O3) ratio, n (SiO2)/n(Al2O3) ratio and crystallization time, etc. on the crystalline phase of the product was investigated. When the following molar ratios of the reaction mixture, n (SiO2)/n (Al2O3) 4-10, n[(TMA)2O+Na2O]/ n (Al2O3 ) > 7, n (Na2O)/n (Al2O3)=0. 5-2. 0, n (H2O)/ n(A12O3)=80-450, were used, pure zeolite ZK-4 could be obtained. The synthetic products were characterized by X-ray powder diffraction, atomic absorption spectrophotometry (AAS), adsorption measurement, thermogravimetric analysis(TGA), and 29Si magic angle spinning nuclear magnetic resonance technique. Zeolite ZK-4 has a higher thermal stability than sodium zeolite A due to higher n(Si)/n(Al) ratio of zeolite ZK-4.

Synthesis of Single Crystals of Zeolite Betaby Using Two Silica Sources

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Synthesis of ZSM-5 zeolite membranes without organic templates using a varying-concentration technique

Template-free nanosized ZSM-5 seeds with an average size of 15 nm were prepared from a synthesis solution with the composition 12Na2O∶100SiO2∶2Al2O3∶2500H2O. By the use of these seeds, thin ZSM-5 zeolite membranes were prepared on the outer surface of a porous α-alumina tube with a pore size of 2 μm in a gel system by varying-concentration synthesis with organic-free template. The first composition synthesis sol-gel was the same as seeds of molar composition and the second one was 12Na2O∶100SiO2∶2Al2O3∶5000H2O at 180 ℃ for 10 h, respectively. XRD shows that the film consists of well-crystallized ZSM-5 zeolite. SEM investigation indicats that the zeolite films on the supports are defect free and the film thickness is approximately 8 μm. The permeances for H2, N2, CH4 and CO2 are 8.94×10-7, 3.27×10-7, 3.9×10-7, 3.14×10-7 and 0.874×10-7 mol·m2·s-1·Pa-1, respectively. The ideal selectivity of membrane at room temperature for H2/CO2, H2/N2, H2/CH4 are 2.84, 2.73 and 2.29, respectively.

Synthesis, characteristics of hierarchical EU-1 zeolite for xylene isomerization probe reaction

Introduced a method of synthesizing hierarchical EU-1 zeolite with organosilanes as additive, and studied the influences of following different kinds of organosilanes on the synthesis of hierarchical EU-1 zeolite: γ-glycidoxy propyl trimethoxy silane(GPTMS), N-β-(aminoethyl)-γ-aminopropyl methyl dimethoxyl silane(APAEDMS),and N-(β-aminoethyl)-γ-aminopropyl dimethoxyl(ethyoxyl) silane(TMPED). The hierarchical EU-1 samples were characterized by XRD, SEM, N_2 adsorption, FT-IR and NH_3-TPD to analyze the crystallinity, morphology, surface area, pore size distribution and acidity. The results showed that hierarchical EU-1 zeolites were successfully synthesized; organosilanes have great influence on crystal morphology of EU-1 zeolites; the exterior surface area of hierarchical EU-1 zeolite, which synthesized with organosilanes(APAEDMS) adding into synthesis system, increased by 62.1% and mesopore volume increased by 129.1% compared with conventional EU-1 zeolites, thus can reduce the diffusional restriction markedly in catalytic reaction. The catalytic performance of hierarchical EU-1zeolites were evaluated in m-xylene isomerization on fixed bed reactor. The catalytic data showed that the isomerization activity PX/X of the hierarchical EU-1 zeolites reached around 24.09% in theoretical thermodynamic equilibrium from 23.83%, and the selectivity of C_8 aromatic hydrocarbon increased from 75.16% to 84.87%. The conversion of p-xylene increased from 16.30% to 18.41%.

H-Y-zeolites induced heterocyclization:Highly efficient synthesis of substituted-quinazolin-4(3H) ones under microwave irradiation

A highly efficient synthesis of 2-amino-N-substituted-benzamides was performed by the condensation ofisatoic anhydride with several amines in solvent-free conditions under microwave irradiation. H-Y-zeolites induced heterocyclization of these products with ortho-esters under similar conditions afforded the relevant substituted-quinazolin-4（3H）ones in high yields.

Influence of the fly ash fraction after grinding process on the hydrothermal synthesis efficiency of Na-A,Na-P1,Na-X and sodalite zeolite types

The fly ashes(Class F and C)have been successfully used as the main substrates in the hydrothermal syntheses of Na-A,Na-P1,Na-X and sodalite zeolites.Both ashes and their derivatives after milling with magnetic field grinder were used.The paper investigates the effect of fly ash fraction size on the syntheses efficiency and physicochemical properties of the obtained zeolites.The starting material and obtained zeolites were subjected to physicochemical characteristics using X-ray diffraction,X-ray fluorescence,particle size analysis,and scanning electron microscopy methods.The paper showed a significant effect of the used fly ash fractions on the quantity,purity,quality and level of crystallinity of the zeolites phase obtained.The application of the grinding process prior to the syntheses of zeolites,with a relatively small financial outlay,significantly increases their application potential.Obtained zeolites are a promising material in the context of their use,inter alia,in environmental protection.

Rapid synthesis of ZSM-5 zeolite catalyst for amination of ethanolamine

ZSM-5 zeolite was rapidly synthesized in system containing ethylenediamine from the initial gel: (5-8) Na2O:44 EDA:A12O3:100 SiO2:4000 H2O. The crystals were lath-shaped. The effect of pretreatment and alkalinity on crystallinity was investigated. The pretreatment of silicate source can cut down the crystallization time. Tuning the system alkalinity and controlling crystallization time can ensure forming of pure crystal.

One-Pot Synthesis of Dimethyl Carbonate over Basic Zeolite Catalysts

One-pot synthesis of dimethyl carbonate (DMC) from methanol, propylene oxide (PO) and carbon dioxide has been investigated using the basic zeolites as catalysts. Among the zeolites studied, Beta showed the best catalytic performance for DMC production. That the desilication of zeolite structure resulted in a hierarchical porosity of Beta, leading to more amount of KOH can be loaded on the surface of zeolite and therefore enhancing the base strength of the catalyst was proposed to be the reason for improved catalytic performance.

Hydrothermal Synthesis and Properties of Y-zeolite-containing Composite Material with Micro/mesoporous Structure

有 micro/mesoporous 结构的 Y-zeolite-containing 合成材料从白陶土被综合了借助于在原处结晶化方法。获得的样品被 XRD 调查并且赌了方法。商业 Y 沸石和新奇 Y-zeolite-containing 的催化活动的评估合成材料在脉搏被执行有不同分子的尺寸的二个探查分子的微层析的站台：VGO 化工物品和 1,3,5 tri-isopropyl 苯。Y-zeolite-containing 合成材料富于外部表面和 meso-/macro-pores，这被发现；Y-zeolite-containing 合成材料与商业 Y 沸石相比表明了释放的更小的率。