W. R. Grace Co.-conn.

W. R. Grace Co.

Dean Alexander Denton

Keng-Yu Shih

Michael John Carney

Rimantas Glemza

Raymond D Feldwick

Michael V Ernest

Richard J Nozemack

Richard A Carman

John A Rudesill

The present invention is directed to a novel one-step method for forming a supported catalyst complex of high activity by substantially simultaneously contacting a bidentate or tridentate ligand forming compound, a transition metal compound and a chromium immobilized Lewis acid support-agglomerate. The catalyst can be formed prior to polymerization of olefins or within the polymerization reaction zone.

Chromium support-agglomerate-transition metal polymerization catalysts and processes utilizing same

The present invention is directed to a coordinating catalyst system comprising at least one pre-catalyst selected from late transition metal bidentate or tridentate ligand containing compounds, at least one support-agglomerate having chromium immobilized thereto (e.g., spray dried silica/clay agglomerate), and optionally at least one organometallic compound in controlled amounts, and methods for preparing the same. The resulting catalyst system exhibits enhanced activity for polymerizing olefins and yields polymer products having very good morphology.

Coordination catalyst systems employing chromium support-agglomerate and method of their preparation

A chromium containing catalyst wherein the chromium atom is in one of its higher valence states and is immobilized to a support-agglomerate composed of at least one inorganic oxide component and at least one ion-containing layered component.

Heterogeneous chromium catalysts and processes of polymerization of olefins using same

High melt index polyolefins have been obtained with chromium silica catalysts under conventional polymerization conditions without the use of titanium or other additives. The useful chromium silica catalysts have a pore volume in the range of 1.9-2.9 cc/g and a narrow pore size distribution. The silica is a silica gel preferably obtained from a low solids, rapid gelation process.

High pore volume polyolefin catalyst

The present invention is directed to a coordinating catalyst system comprising at least one metallocene or constrained geometry pre-catalyst transition metal compound, (e.g., di-(n-butylcyclopentadienyl)zirconium dichloride), at least one support-activator (e.g., spray dried silica/clay agglomerate), and optionally at least one organometallic compound (e.g., triisobutyl aluminum), in controlled amounts, and methods for preparing the same. The resulting catalyst system exhibits enhanced activity for polymerizing olefins and yields polymer having very good morphology. The support-activator is a layered material having a negative charge on its interlaminar surfaces and is sufficiently Lewis acidic to activate the transition metal compound for olefin polymerization.

Metallocene and constrained geometry catalyst systems employing agglomerated metal oxide/clay support-activator and method of their preparation

The present invention is directed to a coordinating catalyst system comprising at least one bidentate or tridentate ligand containing pre-catalyst transition metal compound, (e.g., 2,6-bis (2,4,6-trimethylarylamino)pyridyl iron dichloride), at least one support-activator (e.g., spray dried silica/clay agglomerate), and optionally at least one organometallic compound (e.g., triisobutyl aluminum), in controlled amounts, and methods for preparing the same. The resulting catalyst system exhibits enhanced activity for polymerizing olefins and yields polymer having very good morphology.

Coordination catalyst systems employing agglomerated metal oxide/clay support-activator and method of their preparation

Frangible, spray dried agglomerate catalyst supports are provided, e.g. of silica gel, which possess a controlled morphology of microspheroidal shape, rough, scabrous appearance, and interstitial void spaces which penetrate the agglomerate surface and are of substantially uniform size and distribution. The agglomerates also possess a 1-250 micron particle size, 1-1000 m,/gm. surface area, and an Attrition Quality Index (AQI) of at least 10. The agglomerates are derived from a mixture of dry milled inorganic oxide particles, e.g. silica gel, and optionally but preferably wet milled inorganic oxide particles, e.g. silica gel particles, (which preferably contain a colloidal segment of <1 micron particles) slurried in water for spray drying. The high AQI assures that the agglomerates are frangible and that polymerization performance is improved. The controlled morphology is believed to permit the constituent particles of the agglomerates to be more uniformly impregnated or coated with conventional olefin polymerization catalysts.

Frangible, spray dried agglomerated supports, method of making such supports, and olefin polymerization catalysts supported thereon

A method of making frangible, spray dried agglomerate catalyst supports is provided, e.g. of silica gel, which possess a controlled morphology of microspheroidal shape, preferably a rough, scabrous appearance, and interstitial void spaces which penetrate the agglomerate. The agglomerates also possess a 4-250 micron particle size, 1-1000 m,/gm. surface area, and an Attrition Quality Index (AQI) of at least 10. The method comprises dry milling inorganic oxide particles, e.g. silica gel, wet milling the dry milled inorganic oxide particles (to preferably impart a colloidal segment of <1 micron particles), and spray drying the particles. The high AQI assures that the agglomerates are frangible and that polymerization performance is improved. The controlled morphology is believed to permit the constituent particles of the agglomerates to be more uniformly impregnated or coated with conventional olefin polymerization catalysts.

Method of making frangible spray dried agglomerated supports and olefin polymerization catalysts supported thereon

Glycol ether compounds such as glycol ethers and glycol ether esters are used as azeotropic distillation solvents for conversion of inorganic oxide hydrogels to xerogels by removal of water. These compounds are especially useful to make chromium-containing catalysts for production of high melt index polyolefins at reduced cost compared to known azeotropic solvents.

Use of glycol ether compounds for the production of polyolefin catalysts

A method of making chromium containing oxide gel-based catalyst wherein an oxide hydrogel is convened to a xerogel by azeotropic distillation of a mixture of said hydrogel and an organic solvent, the improvement comprising impregnating the gel with a chromium compound during azeotropic distillation by incorporating said chromium compound into said mixture before azeotropic distillation and wherein the organic solvent used is selected from the group consisting of ethoxy ethyl acetate, tert-butyoxy propanol, methoxy propyl acetate, n-butoxy propanol, ethoxy ethyl propionate and mixtures thereof.

Glycol ether compounds for the production of polyolefin catalysts and

Adsorbents are provided which are suitable for use in the removal of contaminants selected from the group consisting of free fatty acids, soaps, phosphorus, metal ions and color bodies. The adsorbents comprise inorganic porous supports selected from the group consisting of substantially amorphous alumina, diatomaceous earth, clays, magnesium silicates, aluminum silicates and amorphous silica, treated with a base in such a manner that at least a portion of said base is retained in at least some of the pores of the support to yield base-treated inorganic porous adsorbents. Processes for removing free fatty acids, etc., from glyceride oils using these adsorbents are also provided.

Use of base-treated inorganic porous adsorbents for removal of

A catalyst for control of hydrocarbon emission with improved resistance to phosphorus, sulfur, halogen and silicon poisoning comprising a refractory oxide support impregnated with 0.5 to 20% by weight chromium oxide or manganese oxide or a mixture thereof, and a catalytically effective amount of one or more platinum group metals. The preferred refractory oxide support is alumina. The preferred platinum group metals include Pt, Pd, Ir and Rh.

Chrome/platinum/palladium catalyst for hydrocarbon emission control

Catalysts and catalyst supports are prepared by forming and drying, preferably spray-drying, an aqueous slurry of inorganic solids such as zeolites, clay, silica, alumina, and silica-alumina gel, and aluminum chlorhydrol to obtain particulate composites. The particulate composites are then reacted with ammonia in the absence of free liquid water to convert the aluminum chlorhydrol into a cohesive binder. The ammonia-reacted composites may then be washed, ion exchanged and thermally activated to obtain active attrition resistant catalysts and catalyst components.

Catalyst manufacture

A catalyst that is especially useful in the production of aromatic nitriles by a fluidized bed process comprises highly attrition-resistant microspherical particles of vanadia and an inert support and is prepared by spray drying an aqueous slurry of finely divided particles of vanadia and the support.

Spray dried vanadia catalyst and method of preparing it

Silica gel pellets are prepared by mixing finely divided silica gel with an aqueous ammoniacal medium, compressing the mixture into pellets, and drying the pellets.

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Baltimore, MD, United States of America

Dean Alexander Denton