The role of pore topology on the behaviour of FCC zeolite additives

Abstract A large variety of zeolite topologies including: large pore tridirectional (Beta), large pore unidirectional (Mordenite, SSZ-24), bidirectional 10 member ring pores (MRP) (ZSM-5), bidirectional 10 × 8 MRP (Ferrierite), tridirectional with connected 12 and 10 MRP (CIT-1), bidirectional with 12 MRP connected by 10 MRP (NU-87), tridirectional with 10 × 11 × 12 MRP (NU-86), and finally 10 MRP, and independent 12 MR cavities connected by 10 MR windows (MCM-22), have been studied as catalysts for the cracking of a gasoline range model molecule ( n -heptane). Kinetic and decay constants as well as selectivity parameters such as paraffin/olefin, i -C 4 / n -C 4 , i -C 5 / n -C 5 , C 3 /C 4…

Can Macroscopic Parameters, Such as Conversion and Selectivity, Distinguish between Different Cracking Mechanisms on Acid Catalysts?

n-heptane cracking has been carried out for very short time periods on an established reaction mechanism which includes the following group of stream reactions on different zeolites: Initiation reactions (protolytic cracking), charge isomerization, chain isomerization, hydride transfer, β-scission–alkylation, desorption–adsorption, and hydrogen transfer–cyclization. It has been observed that a given experimental distribution of products can be explained by more than just one reaction scheme. This does not allow one to clearly distinguish the fraction of reactant which disappears via monomolecular initiation reactions with respect to bimolecular hydride transfer reactions.

Alkylation of Benzene with Short-Chain Olefins over MCM-22 Zeolite: Catalytic Behaviour and Kinetic Mechanism

Abstract Benzene alkylation with ethene and propene has been carried out under liquid-phase reaction conditions over zeolites MCM-22, Beta, and ZSM-5. MCM-22 seems to be a good catalyst for benzene alkylation especially with propene, showing high activity and stability and good selectivity. Kinetic experiments show that alkylation with propene follows an Eley–Rideal type mechanism.

On the Mechanism of Xylene Isomerization and its Limitations as Reaction Test for Solid Acid Catalysts

The kinetics of the gas-phase isomerization of m-xylene, over a series of ultraestable Y zeolites, has been studied in a fixed-bed flow reactor under initial conditions. Using deuterated p-xylene as reactant it has been seen that more than 20% of the m- and o-xylene obtained, are formed via a bimolecular mechanism. The relative proportion of uni- to bimolecular mechanism depends on the zeolite composition. The relation between the turnover number, calculated from the kinetic rate constant for the unimolecular mechanism, and the framework Al content of the zeolite, was coincident with the topological zeolite model. Besides, the values of the adsorption constants indicate that dealumination h…

Cracking Activity and Hydrothermal Stability of MCM-41 and Its Comparison with Amorphous Silica-Alumina and a USY Zeolite

It has been found that the cracking activity of MCM-41 for a reaction catalyzed by strong acids site, such asn-heptane cracking, is much lower than that of a USY zeolite, and similar to that of amorphous silica-alumina. The higher activity of USY is due to the presence of stronger Bronsted acid sites in the zeolite. In the case of gas oil cracking, the greater accessibility of the large molecules to acid sites in MCM-41 relative to USY makes the difference in activity between these two catalysts much smaller than for the pure hydrocarbon. In the calcined state MCM-41 is more active and gives more gasoline and less gases and coke than amorphous silica-alumina. However, when the catalysts wer…

Cracking of n-heptane on a hzsm-5 zeolite. The influence of acidity and pore structure

Abstract The crackino of n-heptane on a HZSM-5 zeolite has been studied in a continuous qlass flow reactor, at atmospheric pressure, up to 470°C. The initial selectivities to the different reaction products, kinetic rate constants, activation energies and decay parameters have been calculated and compared with those obtained using a large pore zeolite (HYUS). A different product distribution is obtained with the two zeolites. In that way, and considering initial selectivities, different C 6 /C 1 , C 5 /C 2 , C 4 /C3, i-C 4 /n-C 4 , ethylene/ethane, propylene/propane ratios have been found on the two zeolite catalysts. The results have been quantitatively explained by considerinq a direct cr…

The skeletal isomerization of but-1-ene catalyzed by theta-1 zeolite

The complete mechanism for the skeletal isomerization of but-1-ene catalyzed by theta-1 zeolite was investigated theoretically by means of DFT calculations, and the influence of the local geometry of the active site and of electrostatic effects on the geometries of the species involved and on activation and reaction energies were analyzed. It was found that whereas the geometry and stability of alkoxide intermediates are strongly influenced by the local geometry of the active site, the ionic transition states are mainly stabilized by electrostatic effects. Both aspects result in a lowering of the activation energies of the elementary steps that form the mechanism and therefore in enhanced r…

Catalytic activity of large-pore high Si/Al zeolites: Cracking of heptane on H-Beta and dealuminated HY zeolites

Abstract The catalytic activity, selectivity, catalyst decay, thermal and hydrothermal stability, and acidity of H-Beta and HY zeolites with Si Al ratios of 7.5 and 10, respectively, have been studied during cracking of n-heptane at 450 °C and atmospheric pressure. It has been found that the H-Beta zeolite is more active and decays more slowly than HY. H-Beta presents a higher steric hindrance for dibranched molecules and therefore its open structure should be smaller than that of HY. A lower hydrogen transfer activity and hydrothermal stability is observed for H-Beta in comparison with the corresponding HY.

A kinetic study of the cracking, isomerization, and disproportionation of n-heptane on a chromium-exchanged Y zeolite

The kinetic rate constants for the cracking, isomerization, and disproportionation of n-heptane over a CrHNaY (32% chromium exchanged) zeolite catalyst at 400, 450, and 470 °C have been calculated. The interaction of n-heptane with a model Lewis acid such as BF3 and progress along the reaction coordinate have been studied by means of molecular orbital calculations. From the kinetic results, i.e., activation energies and frequency factors, and the theoretical calculations, it can be concluded that the controlling step in these reactions is not the formation of the carbonium ion, but the subsequent transformation of this carbonium ion. In addition, the theoretical calculations show that the a…

Catalytic cracking of alkanes on MCM-22 zeolite. Comparison with ZSM-5 and beta zeolite and its possibility as an FCC cracking additive

Abstract N-heptane cracking has been carried out on MCM-22, and its kinetic and decay behaviour is compared with that of ZSM-5 and Beta zeolites. In the case of MCM-22 cracking occurs in the 10-member ring channel system, as well as in the large cavities formed by 12-member rings. Product selectivities show that MCM-22, while presenting features which indicate structural similarities with ZSM-5, it also presents characteristics corresponding to pores or cavities larger than ZSM-5. The selectivities to the individual products together with C1 + C2/iC4, C3/C4, C5/C2, iC4/total C4, and alkane/alkene ratios indicate that MCM-22 has good properties to be used as an FCC octane booster additive sp…

Current views on the mechanism of catalytic cracking

Abstract The cracking mechanisms of hydrocarbons have been reviewed and the kinetic and thermodynamic implications of the different steps, i.e. initiation, chain propagation, and termination, have been discussed. Although the cracking mechanism of olefins and alkylaromatics is well established, the initiation step for the cracking of paraffins is still under debate. The role of Bronsted-type active sites and also the possible influence of extra-framework Al species in the case of zeolite catalysts, especially when commercial feeds and industrial conditions are employed, are presented. The product distribution is determined by the number of propagation events occurring per initiation step, a…

Formation of products responsible for motor and research octane of gasolines produced by cracking The implication of framework Si/Al ratio and operation variables

Abstract An alkane in the range of gasoline fraction ( n -heptane) has been used as a reactant to study the influence of zeolite Y catalyst and process variables (i.e., framework Si Al ratio and procedure of dealumination, time on stream, and contact time) on the formation of products responsible for motor and research octane of gasoline during cracking, namely branched, aromatics, and olefins. It is found that the branched isomers in the C 5 and C 6 fractions appear as primary products and are partly produced by disproportionation, since the ratio of iso to normal compounds is above equilibrium. The ratio of branched to linear products strongly decreases when the number of carbon atoms of …

Hydrocracking ofn-heptane. Study of NiO-MoO3catalysts supported on a HY ultrastable zeolite

The hydrocracking of n-heptane in the temperature range of 573 to 623 K and at 2.45 × 106 Pa pressure has been employed as a test reaction for the study of Ni—Mo bifunctional catalysts supported on a HY ultrastable zeolite. Two groups of catalysts containing 8 and 12 wt% of MoO3 and different amounts of NiO have been studied. In both series a maximum in the activity has been obtained for catalysts with a Ni/Mo atomic ratio of 0.8-1.0. The order of the impregnation of the oxides can have little influence on the activity. The most active catalyst has been obtained when the zeolite is exchanged with NH+4 ions until the Na+ level is less than 2% of the original and calcined at 823 K to obtain a…

Influence of the process variables on the product distribution and catalyst decay during cracking of paraffins

Abstract The influence of the partial pressure of the hydrocarbon, reaction temperature, time on stream and the presence of olefins on the product distribution and the kinetics and decay during the cracking of n-heptane on an REHY zeolite were studied. It was found that the isomerization to cracking ratio depends on the hydrocarbon partial pressure. The active sites for cracking and isomerization are not the same and those for cracking decay faster, the selectivity changing with the degree of decay of the zeolite. The protolytic to β-cracking ratio, and therefore the paraffin to olefin ratio, are a function of the partial pressure of n-heptane. Both reactants and products have a marked infl…

Influence of Pore-Volume Topology of Zeolite ITQ-7 in Alkylation and Isomerization of Aromatic Compounds

The void structure of zeolite ITQ-7 (ISV structure) is discussed on the basis of catalytic reaction tests. The isomerization and disproportionation of meta-xylene, and the alkylation of benzene or toluene with either ethanol or isopropanol, on the acidic zeolite have been used as model reactions. The dimensions of its three-dimensional system of channels, with pores between 6.1 and 6.3 A and with lower tortuosity than those of beta zeolite, favor higher ratios of isomerization to disproportionation of meta-xylene, and of mono- to dialkylated products and iso- to n-propylbenzene during alkylation of benzene. These effects are enhanced with a partially coked ITQ-7.

The Role of the Energetics of Adsorption in Kinetic Studies

Determination of the Pore Topology of Zeolite IM-5 by Means of Catalytic Test Reactions and Hydrocarbon Adsorption Measurements

Abstract The pore topology of a recently synthesized zeolite IM-5 has been determined by means of catalytic test reactions, i.e., n -decane hydroisomerization–cracking, m -xylene isomerization–disproportionation, n -hexadecane isodewaxing, and adsorption–microcalorimetry of molecules with different sizes and shapes ( n -hexane, toluene, m -xylene, and 1,3,5 trimethylbenzene). It has been found that the channel network consists of a system of unidirectional 10 MR with lobes or side pockets, or crossing 10 membered ring pores with a pore diameter somewhat smaller than those in ZSM-5. This structure offers interesting shape selectivity features for catalytic reactions.

Product selectivity effects during cracking of alkanes at very short and longer times on stream

Abstract Cracking of C 7 , C 10 , C 12 and C 14 n-alkanes, over USY, Beta and ZSM-5 zeolites was carried out in a reaction system which allows to obtain instantaneous conversions at very short times on stream. With this system the influence of operation variables, chain length of the paraffin fed, and catalyst structure on product selectivity was established. Positive and negative effects of catalyst decay on product selectivity were obtained, and this behaviour could be simulated by using a deactivation model in which the rate of deactivation depends on the product concentration. It was observed that olefin/paraffin, branched/normal paraffin, branched/normal olefin ratios and aromatic sele…

Cracking behavior of zeolites with connected 12- and 10-member ring channels: The influence of pore structure on product distribution

n-Heptane has been cracked on a CIT-1 zeolite which has connected 12- and 10-member ring (MR) channels, and its behavior was compared with that of MCM-22 with nonconnected 12- and 10-MR channels, and SSZ-24 and BETA with unidirectional and tridirectional 12-MR channels, respectively. The kinetic rate constant is highest for CIT-1, and the decay constant is lowest. From the selectivity point of view, its behavior can be better represented by a system with large cavities (the intersections between the 12- and 10-MR) connected by windows. This gives a behavior typical of that of large pore zeolites. CIT-1 produces a remarkably high selectivity toi-C4, and specially to isobutane. This zeolite s…

ChemInform Abstract: Catalytic Activity of Large-Pore High Si/Al Zeolites: Cracking of Heptane on H-Beta and Dealuminated HY Zeolites

Abstract The catalytic activity, selectivity, catalyst decay, thermal and hydrothermal stability, and acidity of H-Beta and HY zeolites with Si Al ratios of 7.5 and 10, respectively, have been studied during cracking of n-heptane at 450 °C and atmospheric pressure. It has been found that the H-Beta zeolite is more active and decays more slowly than HY. H-Beta presents a higher steric hindrance for dibranched molecules and therefore its open structure should be smaller than that of HY. A lower hydrogen transfer activity and hydrothermal stability is observed for H-Beta in comparison with the corresponding HY.

Mild Hydrocracking of Vacuum Gasoil over NiMo-Beta Zeolite Catalysts: The Role of the Location of the NiMo Phases and the Crystallite Size of the Zeolite

Abstract Mild hydrocracking composite catalysts based on NiMo/γ-Al2O3-Beta zeolite have been prepared and the influence of the location of the NiMo phases has been studied. A good hydrocracking activity and the highest HDS conversion was found during the hydrocracking of a vacuum gasoil with the composite catalyst where the NiMo is located on the alumina component and then mixed with the zeolite in a proportion of 1 : 1 by weight. The crystal size of the beta zeolite had a significative influence on the catalytic behaviour, being better the smaller the crystallite size is. The small crystallite beta-based catalyst displayed a higher hydrocracking activity than conventional USY and silica-al…

Decalin and Tetralin as Probe Molecules for Cracking and Hydrotreating the Light Cycle Oil

Abstract Cracking of tetralin and decalin was carried out over several zeolites to establish the effect of the pore topology of the catalyst on product distribution. These molecules were chosen as probe molecules, because they indicate which catalyst is the best for cracking or hydrotreating the light cycle oil (LCO) fraction, which is obtained directly from fluid catalytic cracking units. A set of zeolites with medium-sized (ZSM-5, MCM-22, ITQ-2), large (USY, Beta), and ultralarge pores (UTD-1), as well as a mesoporous MCM-41, were used as catalysts at 723 K. The results demonstrate that pore size and topology have a strong influence on diffusion, and consequently, on activity and selectiv…

Isomerization of C5–C7 n-alkanes on unidirectional large pore zeolites: activity, selectivity and adsorption features

Abstract The hydroisomerization–hydrocracking of nC5–nC7 is studied with a 12MR unidirectional zeolite (ITQ-4). Selectivity and kinetic parameters indicate that differences in pore topology are more important than acidity for determining isomerization selectivity. The adsorption of the paraffins is determined by van der Waals interactions.

Theoretical study of the mechanism of branching rearrangement of carbenium ions

Abstract Owing to the practical interest of the acid catalyzed isomerization reactions of hydrocarbons, the mechanism of the branching rearrangements of C 4 H 9 + and C 5 H 11 + carbenium ions has been studied theoretically using ab initio methods which include electron correlation and extended basis sets. It has been found that the protonated cyclopropane-type species does not appear as a common intermediate for these reactions, since it is a transition state and not a minimum on the potential energy surfaces studied. In the case of C 4 H 9 + cation, the protonated methyl-cyclopropane ring is the transition state for the carbon scrambling reaction in the secondary n-butyl cation, while the…

Catalytic Performance of the New Delaminated ITQ-2 Zeolite for Mild Hydrocracking and Aromatic Hydrogenation Processes

Abstract Catalysts based on NiMo and Pt supported on the new delaminated ITQ-2 zeolite have been prepared and their catalytic properties evaluated for the mild hydrocracking (MHC) of vacuum gasoil and aromatic hydrogenation. The results were compared with those obtained using other conventional supports, e.g., silica, γ-alumina, amorphous silica–alumina (25 wt% Al 2 O 3 ), and USY zeolite, all of which contain the same metal loading as the ITQ-2 material. In the case of MHC of vacuum gasoil, NiMo/ITQ-2 displayed a higher hydrocracking activity than NiMo/SiO 2 –Al 2 O 3 and NiMoγ-Al 2 O 3 , and even higher activity than NiMo/USY in the range 375–425°C. Moreover, NiMo/ITQ-2 had a selectivity …

On the mechanism of catalytic isomerization of xylenes. Molecular orbital studies

Abstract On the basis of CNDO/2 molecular orbital calculations, we postulate the following detailed mechanism for the catalytic isomerization of xylenes which explains the initial product distributions and also our previous finding that the reaction is intramolecular: (i) adsorption of xylene on a surface acid site to form a Wheland-type complex; (ii) disrotatory cyclization of the protonated species into a bicyclo[3, 1, 0]hexenyl complex; (iii) migration of the methylene bridge to a new side of the pentagonal ring; (iv) change of the new bicyclic species back into the corresponding Wheland-type complex; (v) desorption of the xylene isomer from the surface of the catalyst. The overall rate …

Comparison of the activity, selectivity and decay properties of lay and hyultrastable zeolites during the cracking of alkanes

Abstract The cracking of n-heptane on LaY ultrastable zeolite has been studied in a continuous glass flow reactor, at atmospheric pressure, up to 470°C. The initial selectivity to cracking, isomerization and disproportionation, kinetic rate constants, activation energies and decay parameters have been calculated and compared with those obtained using a HY ultrastable zeolite as a catalyst. It has been found that the HY ultrastable zeolite is about 7 times more active for cracking, and about 10 times more active for isomerization and disproportionation than the LaY ultrastable zeolite. The protolytic to β-cracking ratio is higher for the HY ultrastable zeolite. The deactivation takes place b…

Hydrogenation of Aromatics in Diesel Fuels on Pt/MCM-41 Catalysts

Abstract The hydrogenation activity of Pt supported on two mesoporous MCM-41 samples differing in their chemical composition has been studied by following the kinetics of the hydrogenation of naphthalene at 225–275°C reaction temperature and 5.0 MPa total pressure and by comparing the kinetic parameters obtained with Pt supported on a mesoporous amorphous silica-alumina (MSA) and other conventional supports, such as commercial amorphous silica-alumina (ASA), zeolite USY, γ-alumina, and silica. The two mesoporous MCM-41 and MSA materials having very high surface areas allowed for a better dispersion of the Pt particles, and they showed a superior overall hydrogenation activity as compared to…

SOFT AND HARD ACIDITY IN ZEOLITES AND ZEOTYPES: EVALUATION AND CATALYTIC IMPLICATIONS

It has been found by Molecular Orbital calculations, that the energy of the LUMO of a zeolite cluster can be used to measure the softness–hardness acidity. It has been found that the higher the framework Si/AI ratio the softer is the acidity. When applied to the alkylation of aromatics, it has been calculated that the higher the framework Si/AI ratio of the zeolite, the more “orbital controlled” will be the reaction, and therefore a higher para to ortho ratio is expected. This has been confirmed experimentally during the alkylation of toluene and m–xylene by methanol on HY zeolites with different framework Si/AI ratio.