Heterogeneous Iron Catalyst Fe/SBA-15 towards sp3 C-O bond activation in the absence of base and additive

A heterogeneous iron-catalyzed (8wt%Fe/SBA-15) mediated direct alkylation of benzyl alcohol with aryl boronic acid in the absence of base and additive via C-O bond activation is demonstrated. This catalyst system led to an efficient Friedel-crafts alkylation reaction. The acidic site in the catalyst system had been confirmed by NH3-TPD, which shows the presence of three different acidic sites viz., weak, moderated, and strong acid sites. The catalyst showed five times recyclable ability.

Heterogeneous Iron Catalyst Fe/SBA-15 towards sp3 C-O bond activation in the absence of base and additive

A heterogeneous iron-catalyzed (8wt%Fe/SBA-15) mediated direct alkylation of benzyl alcohol with aryl boronic acid in the absence of base and additive via C-O bond activation is demonstrated. This catalyst system led to an efficient Friedel-crafts alkylation reaction. The acidic site in the catalyst system had been confirmed by NH3-TPD, which shows the presence of three different acidic sites viz., weak, moderated, and strong acid sites. The catalyst showed five times recyclable ability.

Enhancing Methane Conversion by Modification of Zn States in Co-Reaction of MTA

Limited by harsh reaction conditions, the activation and utilization of methane were regarded as holy grail reaction. Co-reaction with methanol, successfully realizing mild conversion below 450 °C, provides practical strategies for methane conversion on metal-loaded ZSM-5 zeolites, especially for highly efficient Zn loaded ones. However, Zn species, regarded as active acid sites on the zeolite, have not been sufficiently studied. In this paper, Zn-loaded ZSM-5 zeolite was prepared, and Zn was modified by capacity, loading strategy, and treating atmosphere. Apparent methane conversion achieves 15.3% for 1.0Zn/Z-H2 (16.8% as calculated net conversion) with a significantly reduced loading of 1.0 wt.% against deactivation, which is among the best within related zeolite materials. Besides, compared to the MTA reaction, the addition of methane promotes the high-valued aromatic production from 49.4% to 54.8%, and inhibits the C10+ production from 7.8% to 3.6%. Notably, Zn2+ is found to be another active site different from the reported ZnOH+. Medium strong acid sites are proved to be beneficial for methane activation. This work provides suggestions for the modification of the Zn active site, in order to prepare highly efficient catalysts for methane activation and BTX production in co-reaction with methanol.

Facile and Rapid Synthesis of Durable SSZ-13 Catalyst using Choline Chloride Template for Methanol-to-Olefins Reaction

In the current study, a facile and rapid synthesis approach for a SSZ-13 catalyst using choline chloride (CC) as a template was proposed, and the catalytic performance for the methanol-to-olefins (MTO) reaction was examined. With a proper amount of CC addition (i.e., m(CC)/m(SiO2)=0.14), uniform and homogeneously distributed cubic SSZ-13 crystals were obtained within 4 h with lower aggregation. The synthesized catalyst demonstrated excellent porous features with a total specific surface area and mesopore volume of 641.71 m2·g−1 and 0.04 cm3·g−1, respectively. The optimized strong and weak acid sites on SSZ-13 were obtained by regulating the m(CC)/m(SiO2) ratio. The less strong acid sites and a larger amount of weak acid sites in the synthesized catalyst were conducive to the catalytic performance of the MTO reaction under a lower reaction temperature (450 °C). The appropriate acidity and well-developed pore structure of synthesized SSZ-13 could also slow down the carbon deposition rate and, thus, significantly improve the catalytic lifetime of the catalyst. The methanol conversion rate and initial selectivity of light olefin using the synthesized catalyst could maintain over 95% and 50%, respectively, and a lifetime of 172 min was achieved. Although the low olefin selectivity of the synthesized SSZ-13 catalyst was slightly lower than that of the purchased one, its desirable features were thought to have good potential for industrial application.

Acylation of Anisole With Benzoyl Chloride Over Rapidly Synthesized Fly Ash–Based HBEA Zeolite

Stable HBEA zeolite with high surface area and strong acid sites was synthesized from coal fly ash–based silica extract via indirect hydrothermal synthesis. The rapid HBEA hydrothermal crystallization times of 8, 10, and 12 h were achieved through a reduced molar water fraction in the synthesis composition. The HBEA zeolites prepared from fly ash silica extract exhibited well-defined spheroidal-shaped crystal morphology with uniform particle sizes of 192, 190, or 239 nm obtained after 8, 10, or 12 h of synthesis time, respectively. The high surface area and the microporous area of 702 and 722 m2/g were achieved as a function of shorter hydrothermal synthesis durations (10 and 24 h, respectively) compared to 48 or 72 h, which resulted in HBEA zeolites with lower surface areas of 538 and 670 m2/g. Likewise, temperature-programmed desorption measurements of fly ash–based HBEA zeolites revealed the presence of weak and strong acid sites in the zeolite. The submicron crystal sizes with a well-defined porosity of HBEA zeolites enhanced the diffusion of anisole and benzoyl chloride molecules toward the active acid sites and hence showed better conversion and selectivity in acylation products. High conversion of benzoyl chloride with anisole was achieved, reaching up to 83% with a 93–96% selectivity toward 4-methoxyacetophenone.

Combination of Cu/ZnO Methanol Synthesis Catalysts and ZSM-5 Zeolites to Produce Oxygenates from CO2 and H2

Cu/ZnO methanol catalysts were deposited over several ZSM-5 acid zeolites to directly synthesise oxygenates (methanol and dimethyl ether) from a CO2/H2 feed. Catalysts were prepared by two different preparation methodologies: chemical vapour impregnation (CZZ-CVI) and oxalate gel precipitation (CZZ-OG). Chemical vapour impregnation led to Cu/ZnO being deposited on the zeolite surface, whilst oxalate gel precipitation led to the formation of Cu/ZnO agglomerates. For both sets of catalysts a higher concentration of mild and strong acid sites were produced, compared to the parent ZSM-5 zeolites, and CZZ-CVI had a higher concentration of acid sites compared to CZZ-OG. Nevertheless, CZZ-OG shows considerably higher oxygenate productivity, 1322 mmol Kgcat−1 h−1, compared to 192 mmol Kgcat−1 h−1 over CZZ-CVI (ZSM-5(50), 250 ℃, 20 bar, CO2/H2 = 1/3, 30 ml min−1), which could be assigned to a combination of smaller particle size and enhanced methanol mass transfer within the zeolites.

Effect of the Ni/Al Ratio on the Performance of NiAl2O4 Spinel-Based Catalysts for Supercritical Methylcyclohexane Catalytic Cracking

Supercritical methylcyclohexane cracking of NiAl2O4 spinel-based catalysts with varying Ni/Al deficiencies was investigated. Thus, catalysts with Ni content of 10–50 wt.% were prepared by typical co-precipitation methods. The calcined, reduced, and spent catalysts were characterized by X-ray diffraction, O2 temperature-programmed oxidation, NH3 temperature-programmed desorption, N2 physisorption, O2 chemisorption, scanning and transmission electron microscopy, and X-ray fluorescence. The performance and physicochemical properties of the reference stoichiometric Ni3Al7 catalyst differed significantly from those of the other catalysts. Indeed, the Ni-deficient Ni1Al9 catalyst led to the formation of large Ni particles (diameter: 20 nm) and abundant strong acid sites, without spinel structure formation, owing to the excess Al. These acted with sufficient environment and structure to form the coke precursor nickel carbide, resulting in a pressure drop within 17 min. On the other hand, the additional NiO linked to the NiAl2O4 spinel structure of the Al-deficient Ni5Al5 catalyst formed small crystals (10 nm), owing to the excess Ni, and displayed improved Ni dispersion. Thus, dehydrogenation proceeded effectively, thereby improving the resistance to coke formation. This catalytic behavior further demonstrated the remarkable activity and stability of this catalyst under mild conditions (450 °C and 4 Mpa).

Transformation of right-running gasoline fraction and gaskondensate on bimetallic catalysts based on zeolit ZSM-5

Acidic and catalytic properties of bimetallic catalysts based on ZSM-5 zeolite modified with copper, cobalt and boron in the conversion of straight-run gasoline fraction of gas condensate were studied in a flow-through unit at atmospheric pressure, in the absence of hydrogen in the temperature range 350-4300C. It has been established that the introduction of modifiers (Cu, Co, B) into the zeolite leads to a sig-nificant decrease in the strength and concentration of acid sites. An increase in the copper concen-tration in the zeolite to 3.0 wt.% leads to a decrease in the concentration of strong acid sites from 542 to 332 mmol/g. The introduction of 2% Cu/HZSM-5 into the catalyst composition of the second modifier Co in an amount of up to 1.5 wt.% reduces the concentration of strong acid sites to 242 mmol/g. With the additional modification of the bimetallic catalyst 1.0% Co 2% Cu/HZSM-5 with boron in an amount of 0.5-1.5 wt.%, the concentration of strong acid sites further decreases to 112-198 mmol/g. On unmodified zeolite HZSM-5, which has strong acid sites, cracking and aromatization of hydro-carbons mainly take place. Isomerization of n-paraffin hydrocarbons that make up the gas conden-sate is not significant. As a result of the modification of HZSM-5 with copper in the amount of 1.0-3.0 wt. %.There is a significant increase in the catalyzate content of high-octane components: iso-paraffinic and aromatic hydrocarbons. Modification of the catalyst with 2% Cu/HZSM-5 Co in an amount of 0.5-1.0 wt.% increases its isomerizing activity, and additional modification with boron (0.5-1.5 wt.%) leads to an increase in the yield of liquid products. The relationship between the acid-ic and catalytic properties of modified catalysts has been established. The effect of increasing the isomerizing and aromatizing activity of the modified catalysts is associated with the nature, concen-tration of the modifier, and the ratio of weak and strong acid sites. The isomerizing and aromatizing activity of the catalyst is controlled by the nature and concentration of the modifier. The bimetallic catalyst 1.0% Co 2.0 Cu% 1.0% B/HZSМ-5 exhibits the highest activity in upgrading straight-run gasoline fraction of gas condensate, which makes it possible to obtain a gasoline component with an octane number of 86.5 according to IM at 3800C and a yield of 77.8 wt.%.

Methanol Dehydration to Dimethyl Ether over Modified γ-Al2O3 with Acid, Base and Zeolite (NaA and NaX)

The effect of acids, bases, zeolite NaA and zeolite NaX impregnation to g-Al2O3 on the catalyst characteristics and activity against methanol dehydration reaction were investigated. The catalyst characteristics include N2 physisorption, X-ray diffraction (XRD), and temperature-programmed desorption of ammonia (NH3-TPD) in addition to catalytic dehydration of methanol performed in a micro fixed-bed reactor at 270°C and 1 atm. The results of XRD characterization showed no changes related to the modification of alumina over acids, bases, and zeolite NaA and zeolite NaX. Therefore, the modification did not have any effect on the crystalline structure of alumina. The textural and surface acidity of g-Al2O3 changed post addition of acids, bases, zeolite NaA and zeolite NaX. NH3-TPD analysis results demonstrated that synthesized g-Al2O3 has three types of acid sites: weak, medium, and strong; however, the weak acid sites were not observed on alumina catalysts modified phosphate, KOH, zeolite NaA, and zeolite NaX. Furthermore, the concentration of strong acid sites increased in the catalyst containing KOH. The catalytic test results showed that the untreated g-Al2O3 catalyst gave prominent activity in dehydration of methanol compared to the treated catalyst following the number and strength of acid sites.