Co- and Ni-exchanged ferrierite: The contribution of synchrotron X-ray diffraction data to siting of TMIs

High-silica zeolites exchanged with transition metal ions (TMIs) are the subject of great interest for their unusual catalytic activity and selectivity. Structural information like coordination and accessibility of TMIs in zeolites are important factors for understanding their catalytic activity. Siting of TMIs in zeolites is typically obtained by spectroscopic (EXAFS, EPR, UV–vis and IR) and computational methods, as in the case of Co-ferrierite. However, some controversy exists in the literature concerning the model for incorporation of bare Co ions in ferrierite. We show here that the results of our synchrotron X-ray powder diffraction studies on Co- and Ni-exchanged ferrierite (Si/Al = 8.5) are in a good agreement with the model of Co siting based on an indirect spectroscopic approach and help to validate this model. By direct structural evidences, a possible explanation for the larger catalytic activity of Co sites in the main channels of ferrierite can be inferred. A combination of data from in situ XRD continuous monitoring of the Co ion migration during calcination and crystal-chemical considerations allows to device a strategy for the design of optimised co-cations containing Co-ferrierite catalysts.     

Mechanism of the skeletal isomerisation of linear butenes over ferrierite: analysis of side reactions

An investigation of the effect of reaction conditions on product distribution in the skeletal isomerisation reaction of linear butenes has been carried out. The main reaction routes over ferrierite have been identified. Beside the main product isobutene, major by-product formation occurs. The unwanted reactions include dimerisation of butene to form octenes, hydrogen transfer yielding small amounts of saturated C₃ and C₄ hydrocarbons and disproportionation producing propene and pentenes. The most abundant by-products were pentene and propene, though these were not formed in equimolar amounts as could be expected. Oligomerisation experiments of propene over ferrierite produced large amounts of butene and pentene, revealing the presence of adsorbed nonene. The cracking of this surface species to hexene and propene is the most likely reaction route for the excess propene formation. This additional path to propene formation operates mainly at temperatures above 623 K.     

Lewis Base Additives Improve the Zeolite Ferrierite‐Catalyzed Synthesis of Isostearic Acids

Isostearic acids (IA) are highly utilized for industrial purposes especially in the area of biolubricants, such as cosmetics and slip additives for polyolefin and related copolymer films. This study was designed to develop a zeolitic catalysis process for efficient IA production through isomerization of fatty acids. The process utilized zeolite protonated Ferrierite with a small amount of base additive to neutralize (i.e., poison) the acidic sites on the external surfaces of the zeolite particles to prevent side reactions. Of the six base additives examined, the proton sponge combined with the zeolite protonated Ferrierite was found to be the most effective for this isomerization. With only 0.5 wt% proton sponge additive to 5.0 wt% Ferrierite, the dimers were successfully suppressed from 20.6 wt% yield to 2.42 wt% with an IA yield of 83.4 wt% and a 98 % conversion.     

In Situ Delamination of Ferrierite Zeolite and its Performance in the Catalytic Cracking of C4 Hydrocarbons☆

Ferrierite (FER) zeolites were synthesized by solid transformation at different alkalinities (OH?/Al2O3 molar ratios). The in situ delamination of FER zeolites were achieved and their catalytic perform...     

An FT-IR study of the adsorption of aromatic hydrocarbons and of 2,6-lutidine on H-FER and H-ZSM-5 zeolites

The interaction of aromatic hydrocarbons benzene, toluene, o-, m- and p-xylene and of methyl pyridines (in particular 2,6-lutidine) with H-ZSM-5 and H-FER zeolites has been studied. Two different H-ZSM-5 samples with strongly different intensity ratios between the two main OH stretching bands have been used. Benzene, toluene and p-xylene enter easily the cavities and give rise to three different H-bonded complexes. Two of them are strongly bonded while the third is likely a very hindered and distorted one. o-Xylene enters slowly the cavities and m-xylene even more slowly. Faster diffusion occurs at higher temperatures. On the contrary, xylenes do not enter the FER cavities. In spite of its steric hindrance, supposed to be the same of m-xylene, 2,6-lutidine enters fast the ZSM channels and is protonated by the internal sites. On the contrary, it does not enter the FER cavities, but it is protonated too on the external silanols sites. Evidence is provided for some kind of heterogeneity of the internal sites of ZSM-5 zeolite. Additionally, it is concluded that other effects besides the molecular sieving effect may play a role in the access and diffusion of molecules into the zeolite channels.     

In‐Depth Study of Mass Transfer in Nanoporous Materials by Micro‐Imaging

The first application of interference microscopy to monitoring mass transfer in nanoporous materials dates back to late 1970s when Caro and colleagues reported results of investigations of water uptake by LTA type zeolites. It was, however, not before the beginning of the new millennium that the developments in both the measuring technique and computational power have enabled the recording of transient guest profiles during molecular uptake and release under well‐defined conditions, leading to the establishment of a novel access to diffusion studies, now referred to as micro‐imaging. In the present contribution, the thus accessible novel type of information is illustrated by an in‐depth analysis of the uptake kinetics of methanol in an all‐silica ferrierite. In particular, two remarkable experimental findings are reported, which may be tracked back to their microstructural and/or microdynamic origin, namely a pronounced asymmetry in the transient concentration profiles and a slowing down of guest uptake with increasing temperature.     

Siting and Distribution of Framework Aluminium Atoms in Silicon-Rich Zeolites and Impact on Catalysis

Siting of Al atoms in the framework T sites, in zeolite rings and channel/cavity system, and the distribution of Al atoms between single Al atoms and close Al atoms in various Al-O-(Si-O)_n-Al sequences in Si-rich zeolites represent key parameters controlling properties of counter ion species. Framework Al siting and distribution is not random or controlled by simple rules and depends on the conditions of the zeolite synthesis. Al in Al-O-(Si-O)₂-Al in one 6-MR and single Al atoms predominate in Si-rich zeolites and their population can be varied to a large extent. The siting and distribution of framework Al atoms dramatically affect catalytic activity/selectivity both of protonic and transition metal ion-containing zeolite catalysts.     

Pt-loaded zeolites for reducing exhaust gas emissions at low temperatures and in lean conditions

In this study, pure and platinum-loaded zeolites, ZSM-5, Beta, zeolite Y and Ferrierite, were examined for the reduction of NO with propene in lean conditions and at low temperatures. The studies were carried out by utilising the FT-IR technique both in determination of surface species as well as concentrations in the gas flow at reactor outlet. The maximum in the intermediate formation can be observed at the light-off temperatures over all studied catalyst materials. The maximum conversions of NO were reached with 1 wt% Pt-loaded Beta and Y zeolites in excess oxygen. The lowest light-off temperatures of NO as well as propene can be detected also with Beta and Y zeolite catalysts.     

Structure and Brønsted acid sites of ferrierite

The structure of natural ferrierite (from Kamloops Lake) is determined. The space group is not Immm but I222 (no. 23) and its R-factor is 8.6%. All 18 H₂O molecules, Na⁺, and Mg²⁺ ions are successfully assigned [Mg_1.6(Ca_0.1Ba_0.1Na_1.6K_0.4)Al_5.8Si_30.2O₇₂·18H₂O]. The angle of T(41)–O(5)–T(42) is 168° because the O5 site is not located on an inversion center in I222 space group. We also determined Brønsted acid sites. The Al atom distribution in the framework is also discussed and the T(1), T(2), and T(42) [or T(41)]-sites are the most probable sites.