Stable and Selective Dehydrocondensation of Methane Towards Benzene on Modified Mo/HMCM-22 Catalyst by the Dealumination Treatment

A modified Mo/HMCM-22 catalyst by the dealumination treatment (Mo/HMCM-22-D) exhibited remarkable performance for the catalytic dehydrocondensation of methane with a higher selectivity of benzene and a lower selectivity of coke, in comparison with the same Mo catalyst supported on parent HMCM-22 (Mo/HMCM-22). Excellent catalytic stability as well as a high benzene formation rate of 1500 nmol/(g-cat·s) was obtained on a 6%Mo/HMCM-22-D catalyst at 1023 K, 3 atm and 2700 ml/(g·h) owing to the efficient suppression of coke formation. Dealumination of the HMCM-22 zeolite was characterized by XRD, ²⁷Al and ¹H MAS NMR and NH₃-TPD techniques. It was found that the dealumination treatment of HMCM-22 zeolite resulted in an effective suppression of acid sites, particularly the Brønsted acid sites (proton form in Al--O--Si) owing to the removal of tetrahedral framework aluminum, while the microporous structure and the zeolite framework remained unchanged. It was suggested that the stable and selective dehydrocondensation of methane towards benzene is based on the suppression of coke formation owing to the effective decrease of strong Brønsted acid sites by the dealumination treatment of the HMCM-22 zeolite.     

Isomerization of Alpha-pinene Over Acid Treated Natural Zeolite

In this study, isomerization of α-pinene was studied over several acid-treated natural zeolite catalysts rich in clinoptilolite. Zeolite samples were contacted with HCl at different concentrations at 30°C or at 60°C for 3 and 24 hours and tested in isomerization reaction of alpha-pinene. The catalysts prepared were characterized by XRD, nitrogen adsorption, and acidity studies. Acidity strength and the distribution of Lewis and Brönsted acid sites of the catalysts were determined, and their catalytic activities in α-pinene isomerization and selectivities to main reaction products, camphene and limonene, were investigated. Acid treatment improved the selectivity of catalyst samples to camphene, decreasing the selectivity to limonene, probably forcing limonene to secondary reactions at high conversions.

The kinetics of α-pinene consumption was described by first-order kinetics. Two kinetic models were tested for the reaction mechanism and one model was found to give a good correlation between the theoretical and experimental data. In the models, the key intermediate was the pinylcarbonium ion, which was formed irreversibly from α-pinene.

Number and distribution of Lewis and Brönsted acid sites affect the formation of bicyclic and monocyclic products.     

Preparation of Ceria-Zeolite Catalysts by Different Techniques and Its Effect on Selective Catalytic Reduction of NO with NH3 at High Space Velocities

Several zeolite-based catalysts containing Ce³⁺ and/or CeO₂ were prepared by a variety of catalyst preparation techniques like ion exchange, solid-state ion exchange, impregnation and physical mixing and are characterised. Selective catalytic reduction was evaluated using simulated exhaust gas containing NO _x , NH₃, O₂ and H₂O at high space velocities (>180000 h^–1) in the temperature window 150–600 °C. The activity and selectivity in NO _x reduction was found to strongly depend on the charge compensating ions, crystallite size of the zeolite and CeO₂ content in the catalyst. CeO₂ mixed with zeolite having H⁺ or Ce³⁺ co-cations showed benificial effect and increased the NO _x conversion and selectivity. Among the different zeolite materials studied, the structure and the strength and amount of Brønsted acidity did not influence the NO _x conversion.     

Maximum and time stable aromatic yield in the reforming of alkylcyclopentanes over Pt/β zeolites

The reforming of alkylcyclopentanes is performed at 100 psig over various dealuminated zeolite catalysts supporting various amounts of Pt. As a result of the proper balance between the Brønsted acidity and the metal loading, a maximum aromatic yield was found for a dealuminated catalyst with a SiO₂/Al₂O₃ molar ratio of 130 and 0.5 wt% Pt. The activity of this catalyst remained unchanged with time on stream, and the amount of coke deposited on the catalyst was very low. The aromatic selectivity increased slightly in the initial few hours and then reached a constant value. It appears that the aromatic selectivity is enhanced by the deposition of a small amount of coke. The balancing of the acidic and metallic functions of Pt/ zeolite via dealumination and Pt loading provides a useful reforming catalyst.     

Selective Catalytic Reduction of NOx over H-ZSM-5 Under Lean Conditions Using Transient NH3 Supply

The selective catalytic reduction (SCR) of NO _x over zeolite H-ZSM-5 with ammonia was investigated using in situ FTIR spectroscopy and flow reactor measurements. The adsorption of ammonia and the reaction between NO _x , O₂ and either pre-adsorbed ammonia or transiently supplied ammonia were investigated for either NO or equimolar amounts of NO and NO₂. With transient ammonia supply the total NO reduction increased and the selectivity to N₂O formation decreased compared to continuous supply. The FTIR experiments revealed that NO _x reacts with ammonia adsorbed on Brønsted acid sites as NH₄ ⁺ ions. These experiments further indicated that adsorbed -NO₂ ^– is formed during the SCR reaction over H-ZSM-5.     

Development of mesoporous Al,B-MCM-41 materials: Effect of reaction temperature on the catalytic performance of Al,B-MCM-41 materials for the cyclohexanone oxime rearrangement

A series of aluminum–boron–silicate MCM-41 mesoporous materials and their counterparts treated with NH₄F aqueous solution were synthesized and characterized by using XRD, MAS NMR, nitrogen physisorption, DRIFT, TG-DTA, TP/MS and pyridine adsorption. All of the samples showed typical MCM-41 structural and textural properties. ²⁷Al MAS NMR showed that the aluminum environment was mainly four-coordinated and six-coordinated aluminum for non-fluorinated samples and fluorinated ones, respectively. Boron was in the trigonal framework environment at ca. catalytic reaction temperatures and the NH₄F treatment did not affect the boron environment in our Al,B-MCM-41 materials. All of the Al,B-MCM-41 materials studied contained both Brønsted and Lewis acid sites. However, the strong acid Brønsted/Lewis ratios decreased in the fluorinated catalysts. Moreover, the influence of temperature was studied on the cyclohexanone oxime conversion and the product selectivity in the 623–798 K range. Results indicated that temperatures lower than 748 K favored Beckmann rearrangement to -caprolactam, whereas, at higher temperatures the main reaction was cyclohexanone oxime hydrolysis to cyclohexanone. The aluminum–boron–silicate MCM-41 mesoporous materials treated with NH₄F improved both the selectivity to -caprolactam (related mainly to boron content) and their life span (related to their lower ratios of strong Brønsted/Lewis acid sites).     

Composite SBA-15/MFI Type Materials: Preparation, Characterization and Catalytic Performance

SBA-15 type mesoporous molecular sieve was prepared and used as a parent material for synthesis of a SBA-15/zeolite composite. Thus, after addition of an aluminum source into the pristine sample, it was subjected to recrystallization in the water-vapor phase to give the SBA-15/MFI composites. The samples obtained were characterized by XRD, nitrogen sorption, scanning and transmission electron microscopies, ²⁷Al MAS NMR and FT IR. The materials after recrystallization retained their mesoporous character. Characteristics of the material revealed that all the aluminum added was inserted into the final hybrid. As shown by FT IR and NMR, at least some of aluminum was introduced into the nanoparticles of MFI and adopted four-fold coordination, typical for zeolites. Formation of Brønsted acid centres was directly confirmed by IR studies. The catalytic activity was screened in the liquid-phase isomerization of α-pinene. The main products of α-pinene transformations were camphene, limonene and γ-terpinene. The overall selectivity toward camphene + limonene was ca. 90%. Taking into account the low amount of the MFI phase present in a composite sample, calculated initial reaction rate was comparable with other catalytic systems explored in the isomerization of α-pinene.     

Acid-activated organoclays: preparation, characterisation and catalytic activity of polycation-treated bentonites

Samples of SWy-2 and SAz-1 loaded with increasing amounts of the polycation magnafloc 206, [(Me₂NCH₂CHOHCH₂)_n]ⁿ⁺Cl_n, were acid-treated using 6 M HCl at 95°C for 30, 90 and 180 min. The activity of these acid-activated polycation-exchanged clays for the conversion of α-pinene to camphene and limonene was determined and compared with that from clay samples (without polycation) acid-treated in the same manner. Acid treatment of polycation-exchanged bentonites produced hybrid catalysts which enhanced the activity of the clays for the isomerisation of α-pinene to camphene and limonene. The presence of the polycation had a more marked influence on the activity of samples derived from SAz-1 increasing the yield from 25% for acid-activated SAz-1 with no added polycation to 50% camphene for acid-activated polycation-exchanged SAz-1. The increase in yield for corresponding samples derived from SWy-2 was only from 42 to 52%. This enhancement in yield for samples derived from SAz-1 was attributed to the increased hydrophobicity of the polycation loaded clay whilst the comparable yields for SWy-2 in the absence and presence of polycation may suggest that SWy-2 disperses well in the non-polar α-pinene. The total yields (based on α-pinene) for the most active catalysts was between 80 and 90%. These yields are directly comparable with those obtained by others using zeolites and pillared clays although the acid-activated polycation-treated clays were marginally less selective towards camphene.     

Isomerization of α-pinene to camphene

The catalytic isomerization reaction of α-pinene to camphene over a clinoptilolite catalyst was investigated in a batch reactor open to the atmosphere between 130 and 155°C. The catalyst was selective to the isomerization of α-pinene to camphene. The effects of several variables, such as reaction temperature, amount of catalyst, stirring speed and catalyst particle size, on the conversion of α-pinene and selectivity to camphene were determined. The reaction fits a first-order parallel reaction with rate constants of k ₁ = 3.020·10^?2 e ^?33381.6/RT for the production of camphene and of k ₂ = 1.576·10^?2 e ^?31096.53/RT for the production of limonene.     

Hydroisomerization of model FCC naphtha over sulfided Co(Ni)–Mo(W)/MCM-41 catalysts

Deep hydrodesulfurization (HDS) of gasoline generally brings about the saturation of olefins and leads to the serious octane number losses. Conversion of linear olefins to branched ones followed by hydrogenation to isoalkanes would minimize such octane number losses. In this work, MCM-41-supported Co–Mo, Ni–Mo and Ni–W catalysts were prepared by the incipient wetness impregnation method, and compared with an industrial Co–Mo/γ-Al₂O₃ catalyst. The surface acidities were measured by the techniques of microcalorimetry and infrared spectroscopy for the adsorption of ammonia, and probed by the reaction of conversion of isopropanol. The isomerization and hydrogenation of 1-hexene as well as the HDS of thiophene were studied by using model FCC naphtha. It was found that the sulfidation enhanced significantly the surface Brønsted acidity that favored the skeletal isomerization of 1-hexene under the HDS conditions. Since the isomerization and hydrogenation of 1-hexene are the two competition reactions, the catalysts with relatively lower hydrogenation activity may have higher selectivity to the isomerization reactions. The Co–Mo/MCM-41 showed the high selectivity to the skeletal isomerization reactions due to its strong surface Brønsted acidity and the relatively low hydrogenation activity. On the other hand, the Ni–Mo/MCM-41 exhibited high hydrogenation activity and therefore low selectivity to the isomerization reactions although it possessed quite strong surface Brønsted acidity. The Ni–W/MCM-41 exhibited the low activity for the HDS of thiophene and isomerization of 1-hexene due to the poor dispersion of active metals.     

Skeletal isomerization of 1-butene over ferrierite and ZSM-5 zeolites: influence of zeolite acidity

Three ferrierite (FER) and five ZSM-5 (MFI) zeolites with SiO₂Al₂O₃ ratio ranging from 27 to 2000 are tested as catalysts for the skeletal isomerization of 1-butene at 350–450°C and atmospheric total pressure in order to study the influence of acidity and pore structure of zeolite on conversion and selectivity. The catalytic and NH₃ temperature-programmed desorption results from FER and MFI catalysts with the same SiO₂/Al₂O₃ ratio reveal that the pore structure of FER zeolite rather than its acidity may play an important role in achieving high selectivity for the skeletal isomerization of 1-butene to isobutene.     

Preparation of CuY catalyst using CuCl2 as precursor for vapor phase oxidative carbonylation of methanol to dimethyl carbonate

Cu^IY catalyst was prepared by heating the mixture of CuCl₂ and acidic Y zeolite under flowing nitrogen and characterized by TG/DTG, XRD and elementary analysis techniques. The experimental result indicate that when the heating temperature was from 350 °C to 500 °C, the CuCl₂ of the CuCl₂ and acidic Y zeolite mixture sample decompose to CuCl and Cl₂ gas, then the produced CuCl reacted with the Brønsted acid center H⁺ of Y zeolite to form Cu^IY catalyst by the solid-state ion-exchanged reaction. The amount of ion-exchanged Cu^I in the Cu^IY catalyst reached the maximum of 0.1 mol/g when the heating temperature was 650 °C, and the catalyst exhibited the best catalytic activity, the conversion of methanol (C_MeOH), the selectivity and the space-time yield of dimethyl carbonate (S_DMC and STY) reached 4.36%, 74.55% and 97.32 mg/(g h), respectively.     

NO Oxidation Kinetics on Iron Zeolites: Influence of Framework Type and Iron Speciation

Zeolites having MFI, FER and *BEA topology were loaded with iron using solid state cation exchange method. The Fe:Al atomic ratio was 1:4. The zeolites were characterized using nitrogen adsorption, FTIR and DR UV–Vis–NIR spectroscopy. The catalytic activity in NO oxidation and the occurrence of NO _x adsorption was determined in a fixed-bed mini reactor using gas mixtures containing oxygen and water in addition to NO and NO₂ and temperatures of 200–350 °C. Under these reaction conditions, the NO _x adsorption capacity of these iron zeolites was negligible. The kinetic data could be fitted with a LHHW rate expression assuming a surface reaction between adsorbed NO and adsorbed O₂. The kinetic analysis revealed the occurrence of strong reaction inhibition by adsorbed NO₂. FER and MFI zeolites were more active than *BEA type zeolite. MFI zeolite is most active but suffers most from NO₂ inhibition of the reaction rate. FTIR and UV–Vis spectra suggest that isolated Fe³⁺ cations and binuclear Fe³⁺ complexes are active NO oxidation sites. Compared to the isolated Fe³⁺ species, the binuclear complexes abundantly present in the MFI zeolite seem to be most sensitive to poisoning by NO₂.     

Niobium oxide acidity studied by proton broad-line NMR at 4 K and MAS NMR at room temperature

The quantitative study of the Brønsted acidity of niobic acid (Nb₂O₅·xH₂O) using broad-line¹H NMR at 4 K has been performed by interacting niobic acid, pretreated at 573 K under vacuum, with water molecules. The number of oxyprotonated species (H₃O⁺ and H₂O...HO species formed, unreacted acidic OH groups or excess H₂O molecules) deduced from the simulations of the broad-line¹H NMR spectra shows a continuous increase in the number of H₃O⁺ species with adsorbed water molecules. This increase may be due to a classical dilution effect or to a synergistic interaction between Brønsted and Lewis acid sites. These results are compared with those of some HY zeolites with or without framework defects.     

The catalytic and acidic properties of an i‐Pr2NH‐templated SAPO‐11 and dealuminated derivatives

Crystalline silicoaluminophosphate (SAPO‐11) samples were synthesized with i‐Pr₂NH as a novel template, then dealuminated in H₄EDTA solution. These samples were characterized by catalytic skeletal isomerization of linear butylenes, IR analysis of adsorbed pyridine and ³¹P, ²⁹Si MAS‐NMR. Strong acid sites were concerned with Si domains, that were formed by either increasing the Si content of SAPO‐11 via a synthesis process or dealuminating treatment of as‐synthesized SAPO‐11. Acid sites of medium strength were located around isolated Si together with adjacent Al and the second nearest element P. Deep dealumination led to amorphous AlPO₄, and reduced crystallinity degree. The maximum yield of isobutylene in catalytic skeletal isomerization of linear butylenes were achieved around 763 K. It was confirmed that these reactions were mainly performed on Brønsted acid sites of medium strength.     

Study of the Keggin structure and catalytic properties of Pt-promoted heteropoly compound/Al-MCM-41 hybrid catalysts

Aluminum-containing mesoporous molecular sieves (referred as WSAn, where n = Si/Al molar ratio = 50, 30 and 10) were synthesized via a surfactant templated approach by using fumed silica and aluminum sulfate as Si and Al precursors, respectively. When the 12-tungstophosphoric acid was grafted onto the surface of WSAn, a high dispersion of the heteropolyacid was achieved on the heteropoly compound/WSAn hybrid catalysts. The Keggin structure of the dispersed 12-tungstophosphoric acid was primarily preserved without destruction, but it was distorted in some degree, as confirmed by FTIR, ³¹P NMR-MAS and UV–vis spectroscopic characterizations. The surface Brönsted acidity of the catalysts was greatly enhanced by several times in comparison to that of the bare WSAn support. In the hydroisomerization reaction of n-heptane, the Pt/H₃PW₁₂O₄₀/WSA30 catalyst exhibited the highest catalytic activity and the best isomerization selectivity among the catalysts tested, which can be generally correlated with its large number of Brönsted acid sites and high structural regularity. After the n-heptane hydroisomerization reaction, a high molar ratio of multibranched to monobranched isohexanes was obtained, indicating that Pt-promoted heteropoly compound/WSAn hybrid catalysts have a great potential for the hydroisomerization of long carbon chain hydrocarbons.     

A pronounced catalytic activity of heteropoly compounds supported on dealuminated USY for liquid-phase esterification of acetic acid with n-butanol

12-Phosphotungstic acid and its cesium salts supported on a dealuminated ultra-stable Y zeolite were prepared, and showed the high catalytic activity in the liquid-phase esterification of acetic acid with n-butanol. The supported Cs_2.5H_0.5PW₁₂O₄₀ catalyst gave a high conversion of n-butanol of 94.6% and a selectivity for n-butyl acetate of 100%, accompanying the high water-tolerance and catalytic reusability without regeneration.     

Evaluation of Fe- and Cr-containing clinoptilolite catalysts for the production of camphene from α-pinene

The catalytic properties of the Cr³⁺- and Fe³⁺-loaded clinoptilolites were screened in the liquid-phase isomerization of α-pinene and the major products were found to be camphene and limonene. Selectivity to camphene was superior for the 0.7Fe-CL catalyst than those observed for the Raw-CL and 0.4Cr-CL catalyst. Over raw clinoptilolite, the proportion of limonene and other isomers reached ～65% while it was ～15% with 0.7Fe-CL and ～56% with 0.4Cr-CL. The results also show that the selectivity to camphene increases with increasing reaction time reaching up to about ～72% at 428 K over 0.7Fe-CL catalyst.     

Comparison of the acidity of dealuminated and non-dealuminated HY zeolite by two1H-NMR methods: wide line at 4 K and high resolution MAS at 300 K

¹H-Wide-Line and MAS-NMR at 4 and 300 K, respectively, for HY zeolite samples, non-dealuminated and partially dealuminated with (NH₄)₂SiF₆ reveal significant differences.     

ZrO<Subscript>2</Subscript>–SiO<Subscript>2</Subscript> Mixed Oxides Xerogel and Aerogel as Solid Acid Catalysts for Solvent Free Isomerization of α-Pinene and Dehydration of 4-Methyl-2-Pentanol

Abstract  

Sulfated and non-sulfated ZrO₂–SiO₂ mixed oxide xerogel and aerogel samples having varied Zr/Si molar ratio were evaluated as solid acid catalysts for the isomerization of α-pinene and dehydration of 4-methyl-2-pentanol. Sulfation resulted into enhancement in the catalytic activity of both xerogel and aerogel samples towards the studied reactions. For example, sulfated catalysts showed 86–98% conversion of α-pinene and 8–35% conversion of 4-methyl-2-pentanol. The selectivity data for camphene and limonene indicated the requirement of moderate acidity. The correlation with cyclohexanol dehydration showed that isomerization of α-pinene is a Br?nsted acid catalyzed reaction. The relationship of 4-methyl-2-pentanol conversion with acid site density and sulfur per unit area was found to be linear.