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.

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.

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.

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.

A facile solvent-free synthesis strategy for Co-imbedded zeolite-based Fischer-Tropsch catalysts for direct gasoline production

A series of Co-imbedded zeolite-based catalysts were synthesized following a facile solvent-free grinding route.The catalytic performance for direct syngas conversion to gasoline range hydrocarbons was compared with their counterpart Co-impregnated zeolite-based catalysts.Successful transformation of solid raw materials to targeted zeolite was confirmed by XRD,SEM,STEM,and N2 physisorption analysis.An in-depth study of acidic strength and acidic site distribution was conducted by NH3-TPD and Py-IR spectroscopy.Acidic strength showed a pivotal role in defining product range.Co@S1,with the weakest acidic strength of silicalite-1 among three types of zeolites,evaded over-cracking of product and exhibited the highest gasoline and isoparaffin selectivity(≈70%and 30.7%,respectively).Moreover,the solvent-free raw material grinding route for zeolite synthesis accompanies several advantages like the elimination of production of wastewater,high product yield within confined crystallization space,and elimination of safety concerns regarding high pressure due to the absence of the solvent.Facileness and easiness of the solvent-free synthesis route together with promising catalytic performance strongly support its application on the industrial scale.

Eco-friendly synthesis of high silica zeolite Y with choline as green and innocent structure-directing agent

Zeolite synthesis in contemporary chemical industries is predominantly conducted using organic structure‐directing agents(OSDAs),which are chronically hazardous to humans and the environment.It is a growing trend to develop an eco‐friendly and nuisanceless OSDA for zeolite synthesis.Herein,choline is employed as a non‐toxic and green OSDA to synthesize high silica Y zeolite with SiO2/Al2O3 ratios of 6.5–6.8.The prepared Y zeolite samples exhibited outstanding(hydro)thermal stability at ultrahigh temperature owing to the higher SiO2/Al2O3 ratio.The XRF,SEM,29Si‐NMR and 13Na+results suggested that choline plays a structure‐directing role in the synthesis of Y zeolite,while the feed molar fraction of Na+is a crucial determinant for the framework SiO2/Al2O3 ratio and the crystal morphology.

Synthesis of mesoporous high‐silica zeolite Y and their catalytic cracking performance

Mesoporous high‐silica zeolite Y with advantages of improved accessibility of acid sites and mass transport properties is highly desired catalytic materials for oil refinery,fine chemistry and emerg‐ing biorefinery.Here,we report the direct synthesis of mesoporous high‐silica zeolite Y(named MSY,SiO_(2)/Al2O_(3)≥9.8)and their excellent catalytic cracking performance.The obtained MSY mate‐rials are mesoporous single crystals with octahedral morphology,abundant mesoporosity and ex‐cellent(hydro)thermal stability.Both the acid concentration and acid strength of H‐form MSY are obviously higher than those of commercial ultra‐stable Y(USY),which should be attributed to the uniform Al distribution of MSY zeolite.The H‐MSY displays an obviously reduced deactivation rate and improved catalytic activity in the cracking reaction of bulky 1,3,5‐triisopropylbenzene(TIPB),as compared with its mesoporogen‐free counterpart and USY.In addition,H‐MSY was investigated as catalyst for the cracking of industrial heavy oil.The MSY‐based catalyst(after aging at 800 oC in 100%steam for 17 h)exhibits superior conversion(7.64%increase)and gasoline yield(16.37%increase)than industrial fluid catalytic cracking(FCC)catalyst under the investigated conditions.

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:Al2O3:100 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.

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.

Straightforward synthesis of beta zeolite encapsulated Pt nanoparticles for the transformation of 5-hydroxymethyl furfural into 2,5-furandicarboxylic acid

Encapsulating noble metal nanoparticles(NPs)within the zeolite framework enhances the stability and accessibility of active sites;however,direct synthesis remains a challenge because of the easy precipitation of noble metal species under strong alkali crystallization conditions.Herein,beta zeolite-encapsulated Pt NPs(Pt@Beta)were synthesized via a hydrothermal approach involving an unusual acid hydrolysis preaging step.The ligand—(3-mercaptopropyl)trimethoxysilane—and Pt precursor were cohydrolyzed and cocondensed with a silica source in an initially weak acidic environment to prevent colloidal precipitation by enhancing the interaction between the Pt and silica species.Thus,the resultant 0.2%Pt@Beta was highly active in the transformation of 5-hydroxymethylfurfural into 2,5-furandicarboxylic acid(FDCA)under atmospheric O2 conditions by using water as the solvent while stably evincing a high yield(90%)associated with a large turnover number of 176.The excellent catalysis behavior is attributable to the enhanced stability that inhibits Pt leaching and strengthens the intermediates that accelerate the rate-determining step for the oxidation of 5-formyl-2-furan carboxylic acid into FDCA.

Insights into the Organotemplate-Free Synthesis of Zeolite Catalysts

As the most important nanoporous material, zeolites, which have intricate micropores, are essential heterogeneous catalysts in industrial processes. Zeolites are generally synthesized with organic templates under hydrothermal conditions; however, this method is environmentally unfriendly and costly due to the formation of harmful gases and polluted water. This article briefly summarizes the role of organic templates and describes designed routes for the organotemplate-free synthesis of zeolites, aided by zeolite seeds and zeolite seeds solution. Furthermore, this review explicates that the micmpore volume decreases with an increase of the Si/Al ratios in the organotemplate-free synthesis of zeolite products, where Na^＋ exists as an alkali cation. This feature is very important in directing the synthesis of zeolite catalysts with controllable Si/AI ratios under organotemplate-free conditions, and is thus important for the efficient design of zeolites.

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%.

Organotemplate-free Hydrothermal Synthesis of SUZ-4 Zeolite: Influence of Synthesis Conditions

Various conditions were investigated in detail for the novel organic template-free static hydrothermal synthesis of SUZ-4 zeolite in the presence of seeds. The obtained samples were characterized by XRD （X-ray diffraction）, SEM （scanning electron microscope）, TG （thermal gravimetric analysis）, ICP （inductively coupling plasma） elemental analysis, nitrogen sorption isotherm and surface area. The results show that pure SUZ-4 zeolites with high crystallinity are obtained in a broad window of synthesis conditions： seed mass concentration 0.2%-2%, SIO2/A1203 molar ratio 21 25, KOH/SiO2 molar ratio 0.33 0.43, H20/SiO2 molar ratio 7.14-38.1, aging time 24 h, crystallization temperature 160℃, and crystallization time 6-10 d. Also, crystallinity and size of the rod-like SUZ-4 zeolite crystals are found to alter with the conditions.