Mobil Oil Corporation

Edward J Rosinski

Charles J Plank

Mae K Rubin

Edwin N Givens

Albert B Schwartz

George T Kerr

Hartley Owen

Paul B Venuto

Stuart S Shih

Philip Jay Angevine

Roland H Heck

Francis G Dwyer

Guenter H Kuehl

Thomas R Stein

Ronald H Fischer

Yun-Yang Huang

Harry G Doherty

This invention relates to a new synthetic porous zeolite, characterize as ZSM-45, a method for its preparation and use thereof in catalytic conversion of organic compounds. This crystalline material may have a ratio of XO.sub.2 :Y.sub.2 O.sub.3 of at least 8, wherein X represents silicon and/or germanium and Y represents aluminum, boron, chromium, iron and/or gallium. When X is silicon and Y is aluminum, the new, synthetic zeolite is analogous, in some respects, to the naturally occuring zeolite, levynite. The silica/alumina form of this new crystalline material has a silica to alumina ratio of at least 8 and may be prepared with directing agents which are 2-(hydroxyalkyl) trialkylammonium compounds, dimethyldiethylammonium compounds or cobalticinium compounds. The new crystalline material exhibits a characteristic X-ray diffraction pattern.

Zeolite ZSM-45

A method of producing zeolites particularly ZSM-5 and ZSM-11 by strictly controlling the composition of the forming bath such that no organic is required. In a preferred embodiment the forming bath can contain seeds, lower aliphatic alcohols and/or ammonium hydroxide. The as-crystallized product has no organic in its pore structures and has a relatively low silica to alumina ratio.

Method for producing zeolites

As synthesized by previous methods, ZSM-5 or ZSM-11 zeolites are crystallized in the presence of substantial amounts of a nitrogen-containing compound. When synthesized in this way, they contain an organic ammonium cation as well as a metal cation such as sodium. To obtain a more active form, the sodium ion must be exchanged out. Such exchange, especially with ZSM-5 and ZSM-11, is difficult unless there is calcination of the zeolite to remove the obstructing organo compounds. By making these zeolites in the presence of (1) seeds of the desired zeolite, (2) mixtures of them with ammonium hydroxide and/or alcohol, (3) the alcohol per se or (4) mixtures of the alcohol with ammonium hydroxide, a product substantially deficient in organic ammonium cation is obtained. These products can be exchanged directly without any calcination.

A zeolite, its method of preparation and use is disclosed. The zeolite is characterized by a silica to alumina mole ratio greater than 12 and a Constraint Index of 1 to 12. The zeolite undergoes controlled alumina extraction by treatment with, e.g., strong mineral acid or chelating agent. Removal of aluminum increases the acid activity of the zeolite.

Catalytic cracking with framework aluminum extracted zeolite

A method is provided for enhancing the shape selectivity of a crystalline zeolite having a silica-to-alumina mol ratio greater than 10. The method consists of treating the zeolite with an ammonium fluoride solution at moderately elevated temperature, in the absence or in the presence of a matrix. The products are useful as shape-selective sorbents, and also as shape-selective catalysts for organic reactions including catalytic dewaxing.

Enhancement of shape selectivity of zeolites

Metal poisoning of hydrodesulfurization catalysts is reduced by coating the catalyst surface with a hydrated clay mineral, hydrated alumina, hydrated silica, or mixtures thereof. The catalyst and process in which it is used are particularly useful for the desulfurization of residual oils to produce low-sulfur, fuel oil products.

Hydrodesulfurization process employing poison-resistant catalyst

A process for catalytically cracking a hydrocarbon feed in a reaction zone under catalytic cracking conditions in the absence of added hydrogen with a catalyst comprising a conventional cracking catalyst. The improvement comprises adding to the conventional cracking catalyst a thermally treated zeolite having a mole ratio of SiO.sub.2 :Al.sub.2 O.sub.3 of about 10:1 to 100:1 and a constraint index of about 1 to 12. Thermal treatment reduces the additive zeolite's alpha activity to about 1 to 10 prior to use.

Fluidized catalytic cracking process

A process for increasing gasoline octane number and/or total gasoline yield in catalytic cracking units by the addition of a very small amount of finely divided shape selective additive promoter, which additive promoter is not intimately combined with a substantial amount of another solid prior to contact with the cracking catalyst. The additive promoter is a zeolite characterized by a silica to alumina mole ratio greater than about 500 and a constraint index within the approximate range of 1 to 12.

Promotion of cracking catalyst octane yield performance

Conversion, e.g. dehydration of aliphatic organic oxygenates having up to about 6 carbon atoms by contact with a crystalline aluminosilicate zeolite, preferably ZSM-5, having a silica to alumina ratio substantially greater than 10, at a temperature of about 70.degree. to 1400.degree. F., depending upon the exact nature of the reactant and product.

Conversion of ethers using a zeolite catalyst

The present invention is direction to a unique extrusion die which may be employed in the extrusion of materials wherein a specific desired cross section is sought. The die comprises a center plate and one or more outer annular parts. Shaped holes, from which the material being extruded is emitted, are aligned at the respective edges of the center plate and the surrounding outer annular part. The die may be fabricated utilizing conventional equipment and may be employed to achieve extremely detailed cross sectional configurations of extruded materials.

Extrusion die for shaped extrudate

An improved hydrotreating catalyst, and a process for using thereof, comprises a conventional Group VIA and Group VIIIA metal oxide or metal sulfide, deposited on an inorganic refractory support and about 0.1% by weight to about 7% by weight of the catalyst of a promoter comprising a halogenated metal selected from the Group consisting of halogenated metals of Group IB, IIB, IIIB, titanium and tin. The presence of the promoter results in greater degree of desulfurization and in CCR reduction of hydrocarbon feedstocks, especially highly aromatic petroleum residue and synthetically-derived hydrocarbons, e.g., coal liquids.

Hydrotreating hydrocarbon feedstocks

An improved hydrotreating catalyst, and a process for using thereof, comprises a conventional Group VIA and Group VIIIA metal metal oxide or metal sulfide, deposited on an inorganic refractory support and about 0.1% by weight to about 7% by weight of the catalyst of a promoter comprising a halogenated metal selected from the Group consisting of halogenated metals of Group IB, IIB, IIIB, titanium and tin. The presence of the promoter results in greater degree of desulfurization and in CCR reduction of hydrocarbon feedstocks, especially highly aromatic petroleum residua and synthetically-derived hydrocarbons, e.g., coal liquids.

A new and useful improvement in the method for preparing synthetic crystalline aluminosilicate zeolite ZSM-12 is provided. The improved method comprises synthesizing ZSM-12 in the presence of cyclic quaternary amine halides as templates rather than the conventional template of tetraethylammonium.

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Pedricktown, NJ, United States of America

Edward J Rosinski