Mesoporous fcc catalysts with excellent attrition resistance

Abstract

This application discloses a mesoporous catalyst formed by combining a matrix precursor treated with a polyphosphate, and a metallic oxide treated with a cationic electrolyte. The combined treatment with the polyphosphate and cationic polyelectrolyte yields unexpected improvements in attrition resistance, while maintaining high overall pore volume, even as the ratio of meso pore volume to macro pore volume of the formed FCC catalyst increases.

Description

BACKGROUND OF THE INVENTION[0001]The present invention relates to novel fluid catalytic cracking catalysts comprising microspheres containing Y-faujasite zeolite and having exceptionally high activity and other desirable characteristics, methods for making such catalysts and the use of such catalysts for cracking petroleum feedstocks, particularly under short residence time processes.[0002]Since the 1960's, most commercial fluid catalytic cracking catalysts have contained zeolites as an active component. Such catalysts have taken the form of small particles, called microspheres, containing both an active zeolite component and a non-zeolite component. Frequently, the non-zeolitic component is referred to as the matrix for the zeolitic component of the catalyst. The non-zeolitic component is known to perform a number of important functions, relating to both the catalytic and physical properties of the catalyst. Oblad described those functions as follows: “The matrix is said to act as ...

AI Technical Summary

Benefits of technology

[0026]Improved attrition resistance, as well as controlled pore volume is now provided to an FCC catalyst from a microsphere formed by combining a matrix precursor treated with a polyphosphate and a hydrous kaolin slurry treated with a cationic polyelectrolyte. The combined treatment with the polyphosphate and cationic polyelectrolyte yields unexpected improvements in attrition resistance, while maintaining high overall pore volume, even as the ratio of meso pore volume to macro pore volume of the formed FCC catalyst increases.

Problems solved by technology

As the hydrocarbon feed is cracked in the presence of cracking catalyst to form gasoline and olefins, undesirable carbonaceous residue known as “coke” is deposited on the catalyst.

These cycles of cracking and regeneration at high flow rates and temperatures have a tendency to physically break down the catalyst into even smaller particles called “fines”.

While the initial size of the particles can be controlled by controlling the initial spray drying of the catalyst, if the attrition resistance is poor, the catalytic cracking unit may produce a large amount of the 0-20 micron fines which should not be released into the atmosphere.

Those skilled in the art also appreciate that excessive generation of catalyst fines increases the cost of catalyst to the refiner.

Excess fines can cause increased addition of catalyst and dilution of catalytically viable particles.

For example, such a result is contrary to the prior art disclosures that low pore volumes “can lead to selectivity losses due to diffusional restrictions.”

Thus, while typical FCC catalysts formed by mechanically incorporating the zeolite within a matrix may have been more porous, the reaction time in prior art FCC risers did not yield any advantage in activity or selectivity.

Assertions made to the contrary were inconsistent with the facts and easily dismissed as self-serving.

Several of the designs do not even employ a riser, further reducing contact time to below one second.

The processing of increasingly heavier feeds in FCC type processes and the tendency of such feeds to elevate coke production and yield undesirable products have also led to new methods of contacting the feeds with catalyst.

Unfortunately, it has been found that the API gravity of the bottoms formed during short contact time (“SCT”) often increases after a unit revamp, leading some to suggest that the heaviest portion of the hydrocarbon feed takes longer to crack.

As the porosity of a microsphere is increased, however, the rate at which the microsphere fractures and attrits into finer particles within the FCC unit operating environment increases; resulting in increased fresh catalyst addition rates and increased particulate emission from the unit.

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