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.

Dealuminated Hβ zeolite for selective conversion of fructose to furfural and formic acid

The fructose-to-furfural transformation is facing major challenges in the selectivity and high efficiency. Herein, we have developed a simple and effective approach for the selective conversion of fructose to furfural using Hβ zeolite modified by organic acids for dealuminization to regulate its textural and acidic properties. It was found that citric acid-dealuminized Hβ zeolite possessed high specific surface areas, wide channels and high Brønsted acid amount, which facilitated the selective conversion of fructose to furfural with a maximum yield of 76.2% at433 K for 1 h in the γ-butyrolactone(GBL)-H_(2)O system, as well as the concomitant formation of 83.0% formic acid. The^(13)C-isotope labelling experiments and the mechanism revealed that the selective cleavage of C1–C2 or C5–C6 bond on fructose was firstly occurred to form pentose or C5 intermediate by weak Brønsted acid, which was then dehydrated to furfural by strong Brønsted acid. Also this dealuminized Hβ catalyst showed the great recycling performance and was active for the conversion of glucose and mannose.

EDTA-LDH/zeolite制备及其对重金属离子的吸附

用水热法和焙烧还原法两步合成了乙二胺四乙酸-水滑石/沸石(EDTA-LDH/zeolite)复合材料,并将其用于去除水溶液中的Cd^(2+)、Pb^(2+)、Cu^(2+),系统研究不同条件下EDTA-LDH/zeolite对单一及混合重金属离子溶液中Cd^(2+)、Pb^(2+)、Cu^(2+)的吸附效果与吸附机制。结果表明,当EDTA-LDH/zeolite投加量为0.05 g、重金属离子浓度为1500 mg/L、pH值为6.5、吸附时间为24 h时,EDTA-LDH/zeolite吸附性能最佳。重金属离子间存在竞争吸附,EDTA-LDH/zeolite对Cd^(2+)、Pb^(2+)、Cu^(2+)的最大吸附容量分别为65.33、98.35和108.51 mg/g。去除过程中沉淀作用、表面络合、螯合反应等多种机制协同作用,去除行为均符合Langmuir等温模型与拟二阶动力学模型。

Tungsten incorporated mobil-type eleven zeolite membranes: Facile synthesis and tuneable wettability for highly efficient separation of oil/water mixtures

Tungsten (W) incorporated mobil-type eleven (MEL) zeolite membrane (referred to as W-MEL membrane) with high separation performance was firstly explored for the separation of oil/water mixtures under the influence of gravity.W-MEL membranes were grown on stainless steel (SS) meshes through in-situ hydrothermal growth method facilitated with (3-aminopropyl)triethoxysilane (APTES) modification of stainless steel meshes,which promote the heterogeneous nucleation and crystal growth of W-MEL zeolites onto the mesh surface.W-MEL membranes were grown on different mesh size supports to investigate the effect of mesh size on the separation performance of the membrane.The assynthesized W-MEL membrane supported on 500 mesh (25μm)(W-MEL-500) exhibit the hydrophilic nature with a water contact angle of 11.8°and delivers the best hexane/water mixture separation with a water flux and separation efficiency of 46247 L·m^(-2)·h^(-1)and 99.5%,respectively.The wettability of W-MEL membranes was manipulated from hydrophilic to hydrophobic nature by chemically modifying with the fluorine-free compounds (hexadecyltrimethoxysilane (HDTMS) and dodecyltrimethoxysilane(DDTMS)) to achieve efficient oil-permselective separation of heavy oils from water.Among the hydrophobically modified W-MEL membranes,W-MEL-500-HDTMS having a water contact angle of146.4°delivers the best separation performance for dichloromethane/water mixtures with a constant oil flux and separation efficiency of 61490 L·m^(-2)·h^(-1)and 99.2%,respectively along with the stability tested up to 20 cycles.Both W-MEL-500-HDTMS and W-MEL-500-DDTMS membranes also exhibit similar separation performances for the separation of heavy oil from sea water along with a 20-fold lower corrosion rate in comparison with the bare stainless-steel mesh,indicating their excellent stability in seawater.Compared to the reported zeolite membranes for oil/water separation,the as-synthesized and hydrophobically modified W-MEL membranes shows competitive separation performances in terms of flux and separation efficiency,demonstrating the good potentiality for oil/water separation.

Synthesis of spherical nano-ZSM-5 zeolite with intergranular mesoporous for alkylation of ethylbenzene with ethanol to produce m-diethylbenzene

Catalytic synthesis of m-diethylbenzene(m-DEB)through alkylation of ethylbenzene(EB)may be a promising alternative route in comparison with traditional rectification of mixed DEB,for which the top priority is to develop efficient and stable heterogeneous catalysts.Here,the spherical nano-ZSM-5 zeolite with abundant intergranular mesoporous is synthesized by the seed-mediated growth method for alkylation of EB with ethanol to produce m-DEB.The results show that the spherical nano-ZSM-5 zeolite exhibits better stability and higher alkylation activity at a lower temperature than those of commercial micropore ZSM-5.And then,the spherical nano-ZSM-5 is further modified by La_(2)O_(3) through acid treatment followed by immersion method.The acid treatment causes nano-ZSM-5 to exhibit the increased pore size but decreased the acid sites,and subsequent La_(2)O_(3) loading reintroduces the weak acid sites.As a result,the HNO_(3)-La_(2)O_(3)-modified catalyst exhibits a slight increase in EB conversion and DEB yield in comparison with unmodified one,and meanwhile,it still maintains high m-DEB selectivity.The catalyst after acid treatment achieves higher catalytic stability besides maintaining the high alkylation activity of EB with ethanol.The present study on the spherical nano-HZSM-5 zeolite and its modification catalyst with excellent alkylation ability provides new insights into the production of mDEB.

Production of linear alkylbenzene over Ce containing Beta zeolites

Ce-encapsulated Beta zeolite was synthesized by a one-pot hydrothermal method with citric acid complexing Ce in the absence of Na species.Additional citric acid can effectively prevent the deposition of Ce species during the hydrothermal synthesis of zeolites,leading to uniform distribution of Ce cluster in the framework of Beta zeolites.Moreover,the sodium-free synthesis system resulted that the Brønsted acid sites were mainly located on the straight channels and external surface of Beta zeolites,improving the utilization of Brønsted acid sites.In addition,Ce encapsulated Beta zeolites showed enhanced activity and robust stability in the alkylation of benzene with 1-dodecene based on the synergistic effect between Ce species and Brønsted acid sites,which pave the way for its practical application in the production of alkylbenzene.

Development and Catalytic Cracking Performance of Ultrastable Y Zeolite Rich in Secondary Pores

A novel ultra-stable zeolite, NSZ, rich in secondary pores was developed through the combination of gas-phase andmild hydrothermal methods. This zeolite was successfully tested in an industrial setting for the first time in the world. The porestructure characteristics of the NSZ zeolite prepared for industrial use were analyzed and characterized using BET. The resultsindicate a significant increase in the secondary pore volume of NSZ zeolite compared to the existing ultra-stable zeolite HSZ-5, which is produced through a conventional gas-phase method. The average secondary pore volume to total pore volume ratioin NSZ zeolite was found to be 58.96% higher. The catalytic cracking performance of NSZ zeolite was evaluated. The resultsshowed that the NSC-LTA catalyst, with NSZ as the active component, outperformed the HSC-LTA catalyst with HSZ-5 zeolitein terms of obtaining more high-value products (gasoline and liquefied petroleum gas) during the hydrogenated light cycle oilprocessing. Additionally, the NSC-LTA catalyst showed a significant improvement in coke selectivity.

A concise review on surface and structural modification of porous zeolite scaffold for enhanced hydrogen storage

Investigating zeolites as hydrogen storage scaffolds is imperative due to their porous nature and favorable physicochemical properties.Nevertheless,the storage capacity of the unmodified zeolites has been rather unsatisfactory(0.224%-1.082%(mass))compared to its modified counterpart.Thus,the contemporary focus on enhancing hydrogen storage capacities has led to significant attention towards the utilization of modified zeolites,with studies exploring surface modifications through physical and chemical treatments,as well as the integration of various active metals.The enhanced hydrogen storage properties of zeolites are attributed to the presence of aluminosilicates from alkaline and alkaline-earth metals,resulting in increased storage capacity through interactions with the charge density of these aluminosilicates.Therefore,there is a great demand to critically review their role such as well-defined topology,pore structure,good thermal stability,and tunable hydrophilicity in enhanced hydrogen storage.This article aimed to critically review the recent research findings based on modified zeolite performance for enhanced hydrogen storage.Some of the factors affecting the hydrogen storage capacities of zeolites that can affect the rate of reaction and the stability of the adsorbent,like pressure,structure,and morphology were studied,and examined.Then,future perspectives,recommendations,and directions for modified zeolites were discussed.

Phosphotungstic acid immobilized on amino-functionalized TS-1 zeolite as a solid acid catalyst for the synthesis of tributyl citrate

The amino-functionalization of TS-1 zeolite followed by immobilization of phosphotungstic acid(HPW)was presented to prepare a strong solid acid catalyst for the synthesis of bio-based tributyl citrate from the esterification of citric acid and n-butanol.γ-Aminopropyltriethoxysilane(APTES)was first grafted on the TS-1 zeolite via the condensation reactions with surface hydroxyl groups,and subsequently the HPW was immobilized via the reaction between the amino groups and the protons from HPW-forming strong ionic bonding.The Keggin structure of HPW and MFI topology of TS-1 zeolite were well maintained after the modifications.The amino-functionalization generated abundant uniformly distributed active sites on TS-1 for HPW immobilization,which promoted the dispersity,abundance,as well as the stability of the acid sites.The tetrahedrally coordinated framework titanium and non-framework titania behaved as weak Lewis acid sites,and the protons from the immobilized HPW acted as the moderate or strong Brønsted acid sites.An optimized TBC yield of 96.2%(mol)with a conversion of-COOH of 98.1%(mol)was achieved at 150℃for 6 h over the HPW immobilized on amino-functionalized TS-1.The catalyst exhibited good stability after four consecutive reaction runs,where the activity leveled off at still a relatively high level after somewhat deactivation possibly caused by the leaching of a small portion of weakly anchored APTES or HPW.

High-silica faujasite zeolite-tailored metal encapsulation for the low-temperature production of pentanoic biofuels

Zeolite-encapsulated metal nanoclusters are at the heart of bifunctional catalysts,which hold great potential for petrochemical conversion and the emerging sustainable biorefineries.Nevertheless,efficient encapsulation of metal nanoclusters into a high-silica zeolite Y in particular with good structural integrity still remains a significant challenge.Herein,we have constructed Ru nanoclusters(~1 nm)encapsulated inside a high-silica zeolite Y(SY)with a SiO_(2)/Al_(2)O_(3) ratio(SAR)of 10 via a cooperative strategy for direct zeolite synthesis and a consecutive impregnation for metal encapsulation.Compared with the benchmark Ru/H-USY and other analogues,the as-prepared Ru/H-SY markedly boosts the yields of pentanoic biofuels and stability in the direct hydrodeoxygenation of biomass-derived levulinate even at a mild temperature of 180℃,which are attributed to the notable stabilization of transition states by the enhanced acid accessibility and properly sized constraints of zeolite cavities owing to the good structural integrity.

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 NaY zeolite from a submolten depolymerized perlite:Alkalinity effect and crystallization kinetics

NaY zeolites are synthesized using submolten salt depolymerized natural perlite mineral as the main silica and alumina sources in a 0.94 L stirred crystallizer.Effects of alkalinity ranging from 0.38 to 0.55(n(Na_(2)O)/n(SiO_(2)))on the relative crystallinity,textural properties and crystallization kinetics were investigated.The results show that alkalinity exerts a nonmonotonic influence on the relative crystallinity and textural properties,which exhibit a maximum at the alkalinity of 0.43.The nucleation kinetics are studied by fitting the experimental data of relative crystallinity with the Gualtieri model.It is shown that the nucleation rate constant increases with increasing alkalinity,while the duration period of nucleation decreases with increasing alkalinity.For n(Na_(2)O)/n(SiO_(2))ratios ranging from 0.38 to 0.55,the as-synthesized NaY zeolites exhibit narrower crystal size distributions with the increase in alkalinity.The growth rates determined from the variations of average crystal size with time are 51.09,157.50,46.17 and 24.75 nm·h^(-1),respectively.It is found that the larger average crystal sizes at the alkalinity of 0.38 and 0.43 are attributed to the dominant role of crystal growth over nucleation.Furthermore,the combined action of prominent crystal growth and the longer duration periods of nucleation at the alkalinity of 0.38 and 0.43 results in broader crystal size distributions.The findings demonstrate that control of the properties of NaY zeolite and the crystallization kinetics can be achieved by conducting the crystallization process in an appropriate range of alkalinity of the reaction mixture.

Facile in situ synthesis and characterization of Fe@Si/zeolite Na composites with magnetic core–shell structures from natural materials for enhanced curcumin loading capacity

Curcumin is a natural polyphenol that is used in various traditional medicines.However,its inherent properties,such as its rapid degradation and metabolism,low bioavailability,and short half-life,are serious problems that must be resolved.To this end,a drug carrier incorporating natural magnetic cores in a zeolite framework was developed and applied to the loading of curcumin in ethanol solutions.In this system,curcumin is encapsulated in a zeolite Na(ZNA)magnetic core–shell structure(Fe@Si/ZNA),which can be easily synthesized using an in situ method.Synthesis of Fe_(3)O_(4) nanoparticles was carried out from natural materials using a co-precipitation method.Analysis of the prepared magnetic core–shell structures and composites was carried out using vibrating-sample magnetometery,Fourier transform infrared spectroscopy,transmission electron microscopy,and x-ray diffraction.The cumulative loading of curcumin in the ZNA composite with 9%nanoparticles was found to reach 90.70%with a relatively long half-life of 32.49 min.Stability tests of curcumin loading in the composite showed that adding magnetic particles to the zeolite framework also increased the stability of the composite structure.Adsorption kinetics and isotherm studies also found that the system follows the pseudo-second-order and Langmuir isotherm models.

Synthesis of zeolite A and zeolite X from electrolytic manganese residue,its characterization and performance for the removal of Cd^(2+)from wastewater

Electrolytic manganese residue(EMR)can cause serious environmental and biological hazards.In order to solve the problem,zeolite A(EMRZA)and zeolite X(EMRZX)were synthesized by EMR.The pure phase zeolites were synthesized by alkaline melting and hydrothermal two-step process,which had high crystallinity and excellent crystal control.And the optimum conditions for synthesis of zeolite were investigated:NaOH-EMR mass ratio=1.2,L/S=10,hydrothermal temperature=90℃,and hydrothermal time=6 h.Then,EMRZA and EMRZX showed excellent adsorption of Cd^(2+).When T=25℃,time=120min,pH=6,C0=518 mg·L^(-1),and quantity of absorbent=1.5 g·L^(-1),the adsorption capacities of EMRZA and EMRZX reached 314.2 and 289,5 mg·g^(-1),respectively,In addition,after three repeated adsorption-desorption cycles,EMRZA and EMRZX retained 80%and 74%of the initial zeolites removal rates,respectively.Moreover,adsorption results followed quasi-second-order kinetics and monolayer adsorption,which was regulated by a combination of chemisorption and intra-particle diffusion mechanisms.The adsorption mechanism was ions exchange between Cd^(2+)and Na+.In summary,it has been confirmed that EMRZA and EMRZX can be reused as highly efficient adsorbents to treat Cd^(2+)-contaminated wastewater.

Y Zeolites Modified by Organosilane for Toluene Adsorption under High Humidity Condition

Y zeolites have moderate microporous pore size, large specific surface area, and good hydrothermal stability, which were widely used in industrial adsorption of volatile organic compounds (VOCs), but the performance of Y zeolites in adsorption of VOCs under high humidity conditions is terrible. In this paper, Y zeolites with different silica-alumina ratios were hydrophobically modified by organosilane and characterized by XRD, FTIR, SEM, BET, NMR. In the experiments of static and dynamic adsorption of VOCs by modified Y zeolites, it can be concluded that the static water adsorption capacity of Y zeolites with silica-aluminum ratio of 5 and 40 after silica modification decreased by 62 wt% and 53 wt%, under the conditions of high humidity, GHSV = 15,000 h-1, T = 35°C and initial concentration of toluene C0 = 5000 mg·m-3. The saturation adsorption capacity of toluene was increased from 0.06 g·g-1, 0.09 g·g-1 to 0.15 g·g-1, 0.21 g·g-1, the adsorption selectivity of Y zeolites for water was reduced and that for toluene was increased after Vapor phase silanization overlay modification. The present modification method might carry out targeted modification of zeolites surface, provide research ideas and guidance under high humidity conditions.

Phosphate removal from wastewater by model-La(Ⅲ)zeolite adsorbents

Phosphorus is one of the primary nutrients which leads to eutrophication and accelerates aging process in enclosed water bodies. Because of the poor phosphorus selectivity of other adsorbents, the novel La（Ⅲ）-modified zeolite adsorbent （LZA） was prepared by modifying 90 nm zeolite with lanthanide to selectively remove phosphate in the presence of various omnipresent anions, such as sulfates, bicarbonates, and chlorides. Through batch and fixed bed operation, the following optimum conditions were obtained： concentration of lanthanum chloride solution 0.05 mol/L; solid/liquor ratio 1/25; pH 10; calcination temperature 550℃; time 1 h. The value of the Freundlich model constants Kf and 1/n were found to be 16.76 mg/L and 0.2209, respectively. In addition, when calculated at pH 6.0, distribution coefficient KD could be as high as 36.6. Furthermore, in the alkaline pH range, solution of 0.8 mol/L NaCl was used to regenerate the saturated LZA, which could reach the high regeneration efficiency as high as 100%. Because of the good selectivity and regenerability of LZA, it might serve as a potential way for advanced phosphate removal from the sewage containing other anions.

Removal of Organochlorine from Model Oil Using Mg-Modified ZSM-5 Zeolite:Dechlorination Performance,Regeneration,and Thermodynamics

Various metal-modified ZSM-5 zeolite adsorbents prepared by the impregnation method were applied to the removal of organic chlorides from model naphtha.The adsorption performance and regeneration stability were investigated by static adsorption experiments.The morphologies,structural features,and physicochemical properties of the adsorbents were characterized by X-ray diffraction,Brunauer-Emmett-Teller analysis,NH3 temperature-programmed desorption,scanning electron microscopy,transmission electron microscopy,and pyridine adsorption infrared spectroscopy.The Mg/ZSM-5 zeolite adsorbent possessed a relatively high specific surface area and good metal dispersion and exhibited the best dechlorination and regeneration performance.The characterization results revealed that introduction of the metal exerted a significant influence on the acidic properties of the catalyst surface.A decrease in the ratio of Brønsted acidic sites to Lewis acidic sites and an increase in the amount of moderately acidic sites were confirmed to be responsible for the excellent adsorption performance of the Mg-modified ZSM-5 zeolite.Furthermore,the Langmuir adsorption isotherm model was applied to study the adsorption equilibrium and thermodynamics of the Mg/ZSM-5 adsorbent under mild conditions.The results revealed that the removal of 1,2-dichloroethane by the Mg/ZSM-5 adsorbent was endothermic,spontaneous,disordered,and primarily involved physical adsorption.

Evaluation of zeolites synthesized from fly ash as potential adsorbents for wastewater containing heavy metals

The pure-form zeolites （A and X） were synthesized by applying a two-stage method during hydrothermal treatment of fly ash prepared initial Cu and Zn gel. The difference of adsorption capacity of both synthesized zeolits was assessed using Cu and Zn as target heavy metal ions. It was found that adsorption capacity of zeolite A showed much higher value than that of zeolite X. Thus, attention was focused on investigating the removal performance of heavy metal ions in aqueous solution on zeolite A, comparing with zeolite HS （hydroxyl-solidate） prepared from the residual fly ash （after synthesis of pure-form zeolite A from fly ash） and a commercial grade zeolite A. Batch method was used to study the influential parameters of the adsorption process. The equilibrium data were well fitted by the Langmuir model. The removal mechanism of metal ions followed adsorption and ion exchange processes. Attempts were also made to recover heavy metal ions and regenerate adsorbents.

Ammonium removal by modified zeolite from municipal wastewater

Ammonium removal by modified zeolite, H-form and Na-form zeolite, were examined by batch-type methods. The adsorption of ammonium on modified zeolite was exothermic process. The saturation adsorption capacity of ammonium on H-form and Na-form zeolite were 21.23 and 41.15 mg/g, respectively. After ten times adsorption-desorption-readsorption cycles the standard deviations of H-form and Na-form zeolite were 6.34% and 6.59%. The zeolite adsorption process has proved cost effective and practical in reducing ammonium by H-form and Na-form zeolite in municipal wastewater from concentration 27.68 mg/L to 2.80 mg/L and 5.91 mg/L.