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.

Adsorptive desulfurization over hierarchical beta zeolite by alkaline treatment

Hierarchical beta zeolites with SiO2/Al2O3 molar ratios of 16 to 25 were obtained by alkaline treatment in NaOH solution. The effects of treatment temperature on crystallinity, textural properties and chemical composites were studied by XRD, N2 sorption, FT-IR and XRF techniques. The desulfurization performance of parent and alkaline-treated beta zeolites was investigated by static absorption in four model fuels, containing four sulfur compounds of different molecular sizes like thiophene （TP）, 3-methylthiophene （3-MT）, benzothiophene （BT） and dibenzothiophene （DBT）, respectively. The crystallinity was observed to be successfully maintained when the treatment temperature was below 50 ℃. Mesoporosity of beta zeolite was evidently developed with alkaline treatment. The formation of mesopore remarkably improved the desulfurization performance for TP, 3-MT, BT and DBT, especially for DBT with larger molecular diameter. Though the addition of toluene in the model fuels resulted in a significant drop of the desulfurization performance of mesoporous beta zeolite, the introduction of cerium ions to some extent mitigated the effect of toluene, which means that both the adsorbent’s porous structure and the adsorption mode are responsible for the desulfurization performance. The adsorbent of cerium ion-exchanged mesoporous beta showed about 80% recovery of desulfurization after the first regeneration.

Catalytic performance of Cu-and Zr-modified beta zeolite catalysts in the methylation of 2-methylnaphthalene

2,6-Dimethylnaphthalene(2,6-DMN) is a commercially important chemical for the production of polyethylenenaphthalate and polybutylene naphthalate. However, its complex synthesis procedure and high production cost significantly reduce the use of 2,6-DMN. In this study, the synthesis of 2,6-DMN was investigated with methylation of 2-methylnaphthalene(2-MN) over metal-loaded beta zeolite catalysts including beta zeolite, Cu-impregnated beta zeolite and Zr-impregnated beta zeolite. The experiments were performed in a fixed-bed reactor at atmospheric pressure under a nitrogen atmosphere. The reactor was operated at a temperature range of 400–500 °C and varying weight hourly space velocity between 1 and 3 h^(-1).The results demonstrated that 2,6-DMN can be synthesized by methylation of 2-MN over beta type zeolite catalysts.Besides 2,6-DMN, the product stream also contained other DMN isomers such as 2,7-DMN, 1,3-DMN, 1,2-DMN and 2,3-DMN. The activity and selectivity of beta zeolite catalyst were remarkably enhanced by Zr impregnation, whereas Cu modification of beta zeolite catalyst had an insignificant effect on its selectivity. The highest conversion of 2-MN reached81%, the highest ratio of 2,6-DMN/2,7-DMN reached 2.6 and the highest selectivity of 2,6-DMN was found to be 20% by using Zr-modified beta zeolite catalyst.

Surface dealuminated Beta zeolites supported WO3 catalyst and its catalytic performance in tetralin hydrocracking

In this study,selective dealumination of Beta zeolites was performed through partially removing the templating agent in Beta zeolites by calcination and then removing the aluminum on the external surface of Beta zeolites with acid treatment.Hydrocracking catalysts were prepared by loading WO_(3)onto these dealuminated Beta zeolites.It was shown that the surface SiO_(2)/Al_(2)O_(3)of selectively dealuminated Beta zeolites was higher than that of conventionally dealuminated samples for the same bulk SiO_(2)/Al_(2)O_(3),and the hydrogenation activity of the catalyst of the selectively dealuminated Beta zeolites was lower than that of conventionally dealuminated Beta zeolites.The experimental results for tetralin hydrocracking to BTX showed that the catalysts based on the selectively dealuminated Beta zeolites had higher BTX selectivity and lower coke formation rate than that the catalysts based on the conventionally dealuminated Beta zeolites.

Theoretical Study on a 42 T Model of Beta Zeolite by Density Functional Theory Simulation

Density functional theory was applied to study the structure of Beta zeolite. A model cluster containing 41Si atoms, 1 Al atom, 70 O atoms and 29 H atoms was constructed. The model structures were optimized using the Becke＇s three-parameter hybrid method with the Lee-Yang-Parr correlation functional （B3LYP） and the 6-31G basis set applying the Gaussian03 program package. The NMR parameters were calculated to validate the rationality of the model. It was found that in the optimization models, all O-H bond lengths were in range of 0.984-0.985A^°, among which the model with O-H bond length of 0.98478A^° was more stable than the others. The ^1H and ^27Al chemical shifts of the most stable model were 4.03434 and 55.74 ppm, which were pretty consistent with Larry＇ s experimental data of 4.1 and 54 ppm. The relationship between other structure parameters and total relative electric energy has also been found. All the results exhibit that the 42 T （the total number of Si and Al atoms is 42） model has common properties of the standard of zeolite Beta.

Hydrodeoxygenation of Phenol on Beta Zeolite Catalysts

Biomass is considered the largest renewable energy source and an important alternative for biofuel production. The fast pyrolysis of biomass is an economical and advantageous to get bio-oil. However, bio-oil has a large amount of oxygenated compounds and needs upgrade. The catalytic process of HDO （hydrodeoxygenation） is the most efficient way to remove oxygen from the bio-oil. In this paper, it was studied the HDO phenol （300 ℃ and 35 atm） on catalysts based on cobalt or copper oxides supported on HBeta zeolite. The catalysts were characterized by XRD （X-ray diffraction）, FTIR （infrared spectroscopy） and NH3-TPD （desorption of ammonia）. The results showed the presence of CO304 （cobalt oxide） and CuO （copper oxide）. The measurements showed the presence of acid sites weak, moderate and strong and that the impregnation of the metal oxide modifying the acidity of the support. The results showed the following order HDO conversion： CoHBeta 〉 CuHBeta 〉 HBeta. The presence of the cobalt or copper catalysts contributes to the increase in conversion due to hydrogenation. All catalysts were selective to benzene, but only the impregnated catalysts showed selectivity to cyclohexane and cyclohexene.

THE EFFECT OF ACID TREATMENT ON THE STABILITY OF POLYMORPHS IN BETA ZEOLITE

The stability of beta zeollie in acid solution and the effect of acid treatment on the polymorphs in beta zeolite were studied. This zeolite is easily dealuminated by HCI treatment but its framework highly resistent to acidity.In β zeolite, polymorph A is less stable than polymorph B.The chirality of β zeolite can be modified by the method of acid treatment.

Eco-friendly synthesis and environmental impact assessment of hierarchical Beta zeolite from kaolinite and recycled mother liquor

The development of sustainable techniques to produce high-performance zeolite is essential to achieve green production in industry.Herein,we report an eco-friendly route to synthesizing hierarchical Beta zeolite from kaolinite and recycled mother liquor.The results reveal that the unutilized species(such as silicon species and Na+)in mother liquor stayed in a stable concentration during eleven recycled experiments.Moreover,the synthesized Beta zeolites still have comparable physicochemical properties and catalytic performance in the esterification of levulinic acid with ethanol over the initial zeolite although eleven recycled experiments.Life cycle assessment exhibits that the synthesis of Beta zeolite with recycled mother liquor can reduce global warming potential by 23%and resource depletion-water use by 36%compared to that without recycled mother liquor.This quantitatively demonstrates that the approach proposed in this work is really a sustainable one,extremely increasing the utilization efficiency of raw materials and decreasing the environmental burden.

Synthesis of zeolite Beta containing ultra-small CoO particles for ethylbenzene oxidation

Zeolite Beta containing ultra-small CoO particles was synthesized from a one-step hydrothermal process. The synthesis route involves the pre-mixture of hydrofluoric acid with tetraethylammo- nium hydroxide （in a molar ratio of 1.3-1.5：1） before the addition of a silicon and cobalt source.Investigations by scanning electron microscopy, X-ray diffraction, UV-Vi s spectroscopy, X-ray pho-toelectron spectroscopy, H 2 -temperature-programmed reduct i on and transmi ssi on el ectron mi -croscopy confirm the presence of ultra-small CoO particles in the zeolite Beta structure. The ul-tra-small CoO particles in zeolite Beta present high stability against both oxidation and reduction atmospheres at high temperatures. The catalytic performance of the CoO-containing zeolite Beta catalysts was compared with other Co-containing zeolites by evaluating ethylbenzene oxidation reactivity. The CoO-containing zeolite Beta exhibits high ethylbenzene conversion and high selectiv-ity to acetophenone and 1-phenylethanol. The high activity of this catalyst system can be attributed to the high dispersion of the ultra-small CoO particles in the Beta structure.

Recent Advances of Beta Zeolite in the Volatile Organic Compounds(VOCs)Elimination by the Catalytic Oxidations

Volatile organic compounds(VOCs)have become one of the most serious threats to human health and eco-environment due to their volatility,toxicity and diffusivity,etc.Catalytic completely oxidation had been regarded as a highly efficient strategy for the VOCs abatement.Metal or metal oxides supported on zeolite have been considered as superior catalysts for the treatment of VOCs.Among them,Beta zeolites have attracted many attentions due to their unique structure and consequently catalytic properties in the oxidation of VOCs.The progresses and developments made in the understanding and design of Beta zeolites-based catalysts in the completely oxidation of VOCs in the past two decades have been systematically summarized in this review.

A New Route to Syntheses of Zeolite Beta

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Preparation and Characterization of Zeolite Beta with Low SiO_2/Al_2O_3 Ratio

Zeolite beta with a low SiO2/Al2O3 ratio was synthesizcd by a novel two-step process. The synthesized sample was characterized with XRD, SEM, FTIR, and N2 adsorption-desorption and solid-state MAS NMR. The results showed that aluminium species were inserted into the framework of zeolite beta. The BET surface area, volume, and particle size of the zeolite beta sample decreased with decreasing SiO2/Al2O3 ratio. Our process was proved an efficient route to synthesize zeolitc beta with a low SiO2/Al2O3 ratio.

Crystallization behavior of zeolite beta from acid-leached metakaolin

Well-crystallized zeolite beta was synthesized by using acid-leached metakaolin as the silica-alumina source and tetraethylammonium hydroxide structure-directing agent.The influence of the composition of the reaction mixture on product crystallinity was investigated,and the crystallization process was studied by examining solid samples obtained at different synthesis times.Results showed that the acid-leached metakaolin was fully converted into soluble aluminum and silicon species,which is crucial for the formation of well-crystallized zeolite beta.At the beginning of the crystallization process,these soluble aluminum and silicon species formed a aluminum-rich intermediate structure with layer morphology.With the crystallization proceeding,more silicon species were incorporated into the zeolite beta framework and the layered structure was changed into spherical particles of zeolite beta with high SiO 2 /Al 2 O 3 ratio and crystallinity.

An IR Study on Adsorption of CO and NO on Copper Ion-exchanged Zeolite Beta

Thee adsorption of CO and NO on copper ion-exchanged zeolite Beta was investigated using IR method.It was found that the thermalvacuum pretreatment procedure could result in the reduction of Cu2+ions in zeolite Beta.The adsorption of CO on Cu+sites in zeolite Beta closely follows Langmuir isotherm.Another Cu+species may form during the reaction between water and CO.The catalytic decomposition of NO on the zeolite was observed at room temperature,indicating that the decomposition reaction may occur between two coordinated NO ligands of the same dinitrosyhc complex.Furthermore,the appearance of two series of NO adsorption bands reveals that copper ions existing at different cation sites may have different effect on the adsorption and decomposition of NO molecules.

Cubic Mesoporous Aluminosilicate with Primary Structure Units of Zeolite Beta in the Pore Wall

Mesoporous aluminosilicate with cubic ordered structure was synthesized by two-step crystallization, which showed stronger acid sites and more effective activity for catalytic alkylation of 2, 4-ditert-butylphenol with tert-butanol than conventional H-AlMCM-48 materials.

Ceria-modified hierarchical Hβ zeolite as a robust solid acid catalyst for alkenylation of p-xylene with phenylacetylene

A ceria‐modified hierarchical Hβzeolite was prepared by a desilication‐dealumination procedure followed by ceria modification.The catalytic performance of the ceria‐modified and unmodified hierarchical Hβzeolite catalysts for alkenylation of p‐xylene with phenylacetylene was investigated.Various characterization techniques,including X‐ray diffraction,X‐ray fluorescence,nitrogen adsorption‐desorption,and NH3temperature‐programmed desorption,were used to examine the structure‐performance relationships.Our results show that the optimized ceria‐modified hierarchical Hβzeolite catalyst demonstrated higher catalytic activity,selectivity,and stability for alkenylation of p‐xylene with phenylacetylene than those of pristine Hβzeolite.This performance was attributed to more acidic sites and improved accessibility to active sites through larger pores,together with a higher mesoporous surface area and volume resulting from the hierarchical pore architecture and ceria modification.Thus,our5wt%CeO2‐Hβ‐B0.2A0.2catalyst shows great potential for producing alkenyl aromatics through solid acid catalyzed alkenylation.?2018,Dalian Institute of Chemical Physics,Chinese Academy of Sciences.Published by Elsevier B.V.All rights reserved

Advances in development and industrial applications of ethylbenzene processes

The benzene alkylation process for the production of ethylbenzene has undergone significant improvements during recent decades.Various environmentally benign zeolite-catalyzed ethylbenzene processes,including ZSM-5-zeolite-based vapor-phase ethylbenzene processes and Y-,β-,and MCM-22-zeolite-based liquid-phase processes,have been developed and commercialized.Pure ethylene,ethanol,and dilute ethylene have been used as ethylation agents.Here,the development and industrial application of alkylation catalysts and benzene ethylation techniques are summarized,and some other promising innovations are discussed.Recent advances in benzene alkylation over hierarchical zeolites with improved access to active sites and molecular transport are also covered.Zeolites with short diffusion lengths are promising candidates as better alkylation catalysts.The key point is how to obtain such materials easily and economically.The structure-activity relationships of commercial zeolites in these processes are discussed.Liquid-phase processes catalyzed by β and MCM-22 are more profitable than vapor-phase processes catalyzed by ZSM-5.

Multicolor Photoluminescence in ITQ-16 Zeolite Film

Exploring the native defects of zeolites is highly important for understanding the properties of zeolites, such as catalysis and optics. Here, ITQ-16 films were prepared via the secondary growth method in the presence of Ge atoms. Various intrinsic defects of ITQ-16 films were fully studied through photoluminescence and FTIR characterizations. It was found that both the as-synthesized and calcined ITQ-16 films displayed multicolor photolumines- cence including ultraviolet, blue, green and red emissions by exciting upon appropriate wavelengths. The results in- dicate that Si--OH and non-bridging oxygen hole centers（NBOHCs） are responsible for the origin of green and red emissions at 540--800 nm, while according to a variety of emission bands of calcined ITQ-16 film, blue emission bands at around 446 and 462 nm are attributed to peroxy free radicals（≡SiO2＊）, ultraviolet emissions ranging from 250 nm to 450 nm are suggested originating from a singlet-to-triplet transition of two-fold-coordinated Si and Ge, respectively.