Alkylation Of Mesitylene Research Articles

The effect of amorphous silica support on the catalytic activity of liquid-exfoliated monolayered MCM-56 zeolite

Recently reported groundbreaking discovery of efficient delamination of zeolite MCM-56, producing colloidal suspensions of MWW monolayers dispersed in the liquid phase, created unprecedented possibilities for the synthesis of a zeolite catalyst. Based on this innovation, the concept of using MWW monolayers to prepare silica-supported zeolite nanosheet catalysts suitable for transformations of large organic molecules was explored in this work. A series of silica-MWW preparations was synthesized from colloidal suspensions of the monolayers, using both solid and colloidal silica sources. The synthesized solids were thoroughly characterized with various physicochemical methods and their catalytic performance was tested in alkylation of mesitylene with benzyl alcohol. The obtained results indicate that solids containing MWW layers dispersed on silica show promising catalytic properties. The mixed MWW:silica catalysts synthesized from dispersions of MWW monolayers and liquid silica were found to exhibit high specific catalytic activity (with TOF values of 3.4 × 10−3 to 4.8 × 10−3 s−1), despite the high content of inactive amorphous silica support (40–60%). Materials synthesized from solid fumed and precipitated silicas showed low or negligible overall activity, which could be attributed to the small incorporation of the zeolitic active phase. For one of such materials, a notable high TOF (4.8 × 10−3 s−1) was found. It was found earlier that ethanol is an effective flocculent for zeolite layers by themselves, but in the presence of solid silica its efficiency was reduced.

Exfoliated Ferrierite-Related Unilamellar Nanosheets in Solution and Their Use for Preparation of Mixed Zeolite Hierarchical Structures.

Direct exfoliation of layered zeolites into solutions of monolayers has remained unresolved since the 1990s. Recently, zeolite MCM-56 with the MWW topology (layers denoted mww) has been exfoliated directly in high yield by soft-chemical treatment with tetrabutylammonium hydroxide (TBAOH). This has enabled preparation of zeolite-based hierarchical materials and intimate composites with other active species that are unimaginable via the conventional solid-state routes. The extension to other frameworks, which provides broader benefits, diversified activity, and functionality, is not routine and requires finding suitable synthesis formulations, viz. compositions and conditions, of the layered zeolites themselves. This article reports exfoliation and characterization of layers with ferrierite-related structure, denoted bifer, having rectangular lattice constants like those of the FER and CDO zeolites, and thickness of approximately 2 nm, which is twice that of the so-called fer layer. Several techniques were combined to prove the exfoliation, supported by simulations: AFM; in-plane, in situ, and powder X-ray diffraction; TEM; and SAED. The results confirmed (i) the structure and crystallinity of the layers without unequivocal differentiation between the FER and CDO topologies and (ii) uniform thickness in solution (monodispersity), ruling out significant multilayered particles and other impurities. The bifer layers are zeolitic with Brønsted acid sites, demonstrated catalytic activity in the alkylation of mesitylene with benzyl alcohol, and intralayer pores visible in TEM. The practical benefits are demonstrated by the preparation of unprecedented intimately mixed zeolite composites with the mww, with activity greater than the sum of the components despite high content of inert silica as pillars.

Effect of Si/Al Ratio on the Catalytic Activity of Two‐Dimensional MFI Nanosheets in Aromatic Alkylation and Alcohol Etherification

AbstractZeolite catalysts with pronounced two‐dimensional (2D) morphologies, specifically 2D MFI nanosheets composed of multilamellar stacks of MFI nanosheets, are hypothesized to offer accessibility advantages in catalytic reactions involving large, bulky molecules. The Si/Al ratio of zeolite catalysts is an important parameter determining their performance. However, the effect of Si/Al ratio on catalytic reactivity is not well understood in 2D zeolite catalysts. To provide further insight into this issue, the catalytic performance of 2D MFI nanosheet materials with different Si/Al ratios is compared using the liquid phase Friedel‐Crafts alkylation of mesitylene with benzyl alcohol & the self‐etherification of benzyl alcohol that occurs in parallel, both of which are catalyzed by Brønsted acid sites. The turnover frequency (TOF) of the catalysts is found to decrease with decreasing Si/Al ratio, with the etherification reaction being the main contributor to this trend. When the same reaction is carried out in the presence of a bulky poison, 2,6 di‐tert‐butylpyridine (DTBP), to selectively deactivate the external acid sites, only the etherification reaction of benzyl alcohol takes place in the micropores of the 2D MFI catalyst and the effectiveness factor is found to decrease with decreasing Si/Al ratio. The single component adsorption isotherms of benzyl alcohol show that the uptake normalized per acid site decreases with decreasing Si/Al ratio. Thus, increasing the density of acid sites in the micropores by decreasing the Si/Al ratio makes it more difficult for the reactant molecules to access them, as demonstrated by the decrease in TOF and the effectiveness factor. While the micropore reactions (benzene alkylation, alcohol etherification) showed a clear trend with Si/Al ratio, the reaction catalyzed on the external surface (mesitylene alkylation) did not, showing distinct differences in reactivity.

Dual Template Preparation of MFI Zeolites with Tuning Catalytic Properties in Alkylation of Mesitylene with Benzyl Alcohol

Meso- and microporous ZSM-5 zeolites were synthesized through combination of the tetrapropylammonium hydroxide (TPAOH) and single quaternary ammonium surfactant (Cph–ph–10–6) as dual templates. The structure-directing ability of Cph–ph–10–6 and TPA+ was investigated by density functional theory (DFT) calculation. By tuning the molar ratios of Cph–ph–10–6/TPAOH from 5/0 to 5/8, the structure-directing effects between Cph–ph–10–6 and TPA+ could be systematically modulated, resulting in the morphology of the mesoporous ZSM-5 zeolites changed from ultrathin nanosheets, through splint-like nanosheets, to condensed packing plates. In addition, the hierarchical ZSM-5 zeolites exhibited a greater catalytic activity in alkylation of mesitylene with benzyl alcohol compared with conventional ZSM-5 zeolite. The fine control of meso- and microporous structures of ZSM-5 zeolites by a simple one-step dual template synthesis approach allows the design of the desired catalysts for a green and sustainable future.

Fabrication of meso- and microporous MFI zeolites by amphiphilic molecules with biphenol group

Abstract We reported a strategy to synthesize MFI zeolites with tunable properties by tailoring organic structure-directing agents (OSDAs) under the hydrothermal conditions. The tailored surfactants were obtained by tuning the structure of Gemini-type Cph-10-6-6 and Bola-type BCph-10-6-6, including alkyl tail chains, ammonium groups and alkyl middle chains. The textural property, morphology and acidity of resulting MFI zeolites were characterized by a complementary combination of X-ray diffraction (XRD), scanning electron microscopy (SEM), transmission electron microscopy (TEM), N2 adsorption-desorption isotherms and FTIR spectra of pyridine adsorption. Moreover, the correlation between the OSDAs’ composition and the inorganic precursor in the fabrication of zeolite framework was investigated by DFT calculations in this study. The catalytic performance of the resulting MFI samples was investigated by the alkylation of mesitylene with benzyl alcohol. The results revealed that the OSDAs without ammonium groups only leaded to form the micro-structure of zeolites, but the OSDAs with ammonium groups can induce the formation of micro- and meso-structure simultaneously, regardless the OSDAs ended with or without alkyl tail chains. In addition, the resulting MFI zeolites showed an improved catalytic activity in alkylation of mesitylene with benzyl alcohol due to the enhanced pore accessibility, the acidity (Bronsted/Lewis) controlled the activation of benzyl alcohol, and the ratio of external surface area (Sext/SBET) governed the selectivity of alkylation reaction. As a result, tailoring the structure of OSDAs can pick another strategy to synthesize MFI zeolites with tunable zeolite structure and catalytic performance.

Quantification of external surface and pore mouth acid sites in unit-cell thick pillared MFI and pillared MWW zeolites

The pillared MWW (PMWW or MCM-36) and pillared MFI (PMFI) zeolites consist of a single- or near single-unit-cell thick two-dimensional (2D) zeolitic layer structure. The concentrations of external surface and pore mouth Brønsted acid sites in these zeolites were quantified by a combined dimethyl ether (DME) titration and methanol dehydration in the presence of 2,6-di-tert-butylpyridine (DTBP) or triphenylphosphine (TPP), respectively. DME can access to all Brønsted acid sites in PMFI and PMWW zeolites and thus determine the total number of acid sites. DTBP cannot access to acid sites in micropores, but on the external surface and at the pore mouth regions. In contrast, TPP can only access to acid sites on external surface. The degree of decrease in methanol dehydration rate in the presence of DTBP or TPP indicates the fraction of the sum of external surface and pore mouth acid sites and the sole fraction of external surface acid sites, respectively. The study shows that PMFI contains ∼32% external surface and ∼6% pore mouth acid sites, while PMWW consists of ∼33% external surface and ∼31% pore mouth acid sites. The individual external surface or pore mouth acid site performed distinctively in alkylation of mesitylene by benzyl alcohol reactions.

Effects of the Framework and Mesoporosity on the Catalytic Activity of Hierarchical Zeolite Catalysts in Benzyl Alcohol Conversion

AbstractThe catalytic performance of three‐dimensionally ordered mesoporous imprinted (3DOm‐i) zeolite catalysts with different frameworks (3DOm‐i MFI, 3DOm‐i BEA, and 3DOm‐i LTA) were investigated by the liquid‐phase catalytic conversion of benzyl alcohol in mesitylene and compared to that of other microporous and mesoporous catalysts with a high external surface area, which included MCM‐22, 300 nm MFI, ITQ‐2, and Al‐MCM‐41. The mesoporosity in MFI and BEA zeolites can effectively enhance the catalytic performance of the zeolite catalysts for benzyl alcohol self‐etherification catalyzed by both the acid sites on the external and internal surface and the alkylation of mesitylene with benzyl alcohol catalyzed exclusively by the acid sites on the external surface. For 3DOm‐i LTA, MCM‐22, and Al‐MCM‐41, only the acid sites on the external surface can be utilized in the catalytic reactions. A distinct difference in the product selectivity was also observed for the microporous and mesoporous catalysts.

Friedel-Crafts Alkylation of Mesitylene with tert-Butyl Alcohol over Novel Solid Acid Catalyst UDCaT-5

Alkylation of mesitylene with tert-butyl alcohol in the presence of novel mesoporous superacidic catalysts, namely, UDCaT-4, UDCaT-5 and UDCaT-6 was investigated. The catalysts are modified versions of zirconia showing high catalytic activity, stability and reusability in the presence of water as compared to conventional sulfated zirconia. The catalytic activity is in the order: UDCaT-5 (most active) > UDCaT-6 > UDCaT-4 > sulfated zirconia (S-ZrO2) (least active). The synergistic effect of the very high sulfur content present (9% w/w S) and the preservation of the tetragonal phase in UDCaT-5, in comparison with sulfated zirconia (4% w/w S), were responsible for higher catalytic activity. A catalyst ensuring the production of 2-tert-butyl-mesitylene (2-TBMT) with 98% selectivity and 94% conversion of tert-butanol (TBA) was developed under optimum reaction conditions. The formation of products is correlated with the acidity of the catalyst. The reactions were conducted in liquid phase at relatively low reaction temperatures (120–150 °C). A systematic investigation of the effects of various operating parameters was accomplished and a mathematical model is developed to describe the reaction pathway and validated with experimental results. The reaction was carried out without using any solvent in order to make the process cleaner and greener. An overall second order kinetic equation was used to fit the experimental data, under the assumption that both mesitylene and tert-butanol are weakly adsorbed. An independent dehydration study of tert-butanol (TBA) was also done.

Selectivity engineering in isopropylation of mesitylene with isopropyl alcohol over cesium substituted heteropolyacid supported on K-10 clay

Alkylation of aromatics catalyzed by solid acids constitutes a class of reactions of both academic and industrial importance. Among alkylation reactions, isopropylation of aromatic compounds has attracted considerable attention. Use of propylene as alkylating agent at very high temperatures leads to coke formation which results in deactivation of the catalyst. The use of isopropanol (IPA) as an alkylating agent is attractive when propylene is not readily available. In situ dehydration of IPA leads to prolonged activity since water of reaction suppresses coke formation. Further, IPA dehydration also generates diisopropyl ether which itself is an excellent alkylating agent. Alkylation of mesitylene with propylene or IPA results in the formation of 2-isopropyl-mesitylene (2-IPMT), which is almost extensively used as a precursor in a number of industrial chemicals. This work covers the evaluation of clay-supported heteropolyacids and sulfated zirconia. A variety of solid acid catalysts such as K-10 clay, sulfated zirconia, Filtrol-24, 20% w/w dodecatungstophosphoric acid (H3PW12O40, DTP) supported on K-10 montmorillonite clay and 20% w/w cesium substituted dodecatungstophosphoric acid (Cs2.5H0.5PW12O40, Cs-DTP) supported on K-10 montmorillonite clay were investigated for the liquid phase isopropylation of mesitylene to 2-IPMT using IPA at much milder conditions vis-a-vis other catalysts reported so far. 20% w/w Cs-DTP/K-10 clay was found to be the best catalyst which gives 98% conversion of limiting component, IPA and 98% selectivity towards the desired product, 2-IPMT after 2 h of total reaction time. This catalyst could be reused without any further chemical treatment, eliminating the effluent disposal problems. The reaction was carried out without using any solvent and the process subscribes to the principles of green chemistry. The catalytic activity is in the following order: 20% w/w Cs-DTP/K-10 clay (most active) > 20% w/w DTP/K-10 clay > Filtrol-24 > Sulfated zirconia > K-10 clay (least active). The effect of various operating parameters and catalyst reusability were also systematically investigated. A mathematical model was proposed to probe into the intricate reaction kinetics and mechanism consistent with the experimental results. The reaction is free from any external mass transfer as well as intraparticle diffusion limitations and is intrinsically kinetically controlled. An overall second order kinetic equation was used to fit the experimental data, under the assumption that all the species are weakly adsorbed on the catalytic sites.

Direct evidence α,α-difluorocarbocations in the reactions of chloroacetic acids with sulphur tetrafluoride

Reactions of chloro-, and dichloroacetic acids with sulphur tetrafluoride and p-xylene or mesitylene gave, besides chlorofluoroethanes CF3CH2Cl and CF3CHCl2, small yields of chlorofluoroethylarenes ArCF2CH2Cl and ArCF2CHCl2, and chloroacetylarenes ArCOCH2Cl and ArCOCHCl2 (Ar=p-xylyl or mesityl). With mesitylene, compounds ArCF2CH2Cl and ArCF2CHCl2 are formed exclusively by alkylation of mesitylene with carbocations CH2ClC+F2 and CHCl2C+F2, respectively, while with p-xylene, both, alkylation and the consecutive fluorination of chloroacetyl-p-xylenes with SF4 can contribute to the formation of the corresponding chlorofluoroethyl-p-xylenes.