Chevron Phillips Chemical Company LP

Phillips Petroleum Company

Chevron Philips Chemical Company, LP

Other

Phillips Petroleum

The Shepherd Chemical Company

Williams, Phillips & Umphlett

Chevron Phillips Company, L.p.

Phillips Petroleum Company Washington County

Max P McDaniel

Elizabeth Ann Benham

Qing R Yang

Kathy S Clear

Joel L Martin

Michael D Jensen

Eric D Schwerdtfeger

Kathy S Collins

Gil R Hawley

Tony R Crain

Jeremy M Praetorius

Carlos A Cruz

Marvin M Johnson

Youlu Yu

Ashish M Sukhadia

Jared L Barr

Matthew G Thorn

Anthony P Eaton

Ted H Cymbaluk

Mark L Hlavinka

William Chadwick Ellis

Masud M Monwar

Christopher E Wittner

Steven J Secora

Paul D Smith

Chung Ching Tso

David C Rohlfing

Eric T Hsieh

M Bruce Welch

Alan L Solenberger

Shirley J Martin

Deloris R Gagan

Paul J DesLauriers

Errun Ding

Mitchell D Refvik

Randy S Muninger

Joseph J Bergmeister

Carlton Edwin Ash

Daniel G Hert

Rolf L Geerts

Melvin B Welch

Douglas D Klendworth

Albert P Masino

Guylaine St Jean

Yongwoo Inn

William B Beaulieu

Joseph S Shveima

Syriac J Palackal

Uriah J Kilgore

Rajendra K Krishnaswamy

Randall S Muninger

Helmut G Alt

Scott E Kufeld

Konstantinos Patsidis

Graham R Lief

William R Coutant

James N Short

Brooke L Small

Donald D Norwood

Eduardo J Baralt

Richard M Buck

Kenneth D Hope

Zhihui Gu

John D Hottovy

Bruce E Kreischer

Gary L Glass

Pasquale Iacono

Steven M Bischof

Timothy O Odi

Eric J Netemeyer

Gregory G Hendrickson

H Kenneth Staffin

Fay W Bailey

Simon G Kukes

Bruce B Randolph

Joel A Mutchler

Orson L Sydora

Ronald D Knudsen

Thomas H Smith

Dennis L Holtermann

David H Burns

Donald W Verser

William K Reagen

Timothy W Johnson

Jamie N Sutherland

Kent E Mitchell

Dale A Zellers

Bruce W Gerhold

Kumudini Jayaratne

Donald R Witt

Jared T Fern

James B Kimble

Gerhard P Nowack

Floyd E Farha, Jr

Rex L Bobsein

Richard E Dietz

Jesse R Harris

David R Battiste

Kenneth Farmer

Jeffrey S Lowell

Processes for producing activated chromium catalysts such as chromium/silica catalysts and titanated chromium/silica catalysts are disclosed, and these processes utilize a multistep process involving exposure to inert and oxidizing atmospheres at specific temperature conditions. The resulting activated chromium catalysts have unexpectedly high melt index potential and can produce ethylene-based polymers with lower gel counts in addition to higher melt indices. Related activation systems are provided in which the fluidizing gas entering the fluidized bed vessel can be adjusted between an inert gas, an oxygen-containing gas, or a mixture of the inert gas and the oxygen-containing gas to minimize or prevent exotherms.

Systems and methods for chromium catalyst activation

Processes for producing activated chromium catalysts such as titanated chromium/silica catalysts are disclosed, and these processes utilize a multistep process involving exposure to inert and oxidizing atmospheres at specific temperature conditions. The resulting activated chromium catalysts have unexpectedly high melt index potential and can produce ethylene-based polymers with lower gel counts in addition to higher melt indices.

Methods of chromium catalyst activation to reduce gels and improve melt index potential

Methods for modifying a catalyst system component are disclosed in which a feed mixture containing a fluid and from 1 to 15 wt. % of a catalyst system component is introduced into an inlet of a hydrocyclone, an overflow stream containing from 0.1 to 5 wt. % solids and an underflow stream containing from 10 to 40 wt. % solids are discharged from the hydrocyclone, and the underflow stream is spray dried to form a modified catalyst component. Often, from 4 to 20 wt. % of the catalyst system component in the feed mixture has a particle size of less than or equal to 20 μm, or less than or equal to 10 μm.

Hydrocyclone modification of catalyst system components for use in olefin polymerization

Methods for making titanated silica supports, titanated chromium/silica pre-catalysts, and activated titanated chromium/silica catalysts are disclosed in which hydrogen peroxide and an alkali metal precursor are used during catalyst preparation. Resulting titanated chromium/silica pre-catalysts often contain silica, 0.1 to 5 wt. % chromium, 0.1 to 10 wt. % titanium, and less than or equal to 4 wt. % carbon, and further contain a bound alkali metal or zinc at a molar ratio of alkali metal:titanium or zinc:titanium from 0.02:1 to 3:1 and/or at an amount in a range from 0.01 to 2 mmol of alkali metal or zinc per gram of the silica. High melt index potential activated titanated chromium/silica catalysts can be used to polymerize olefins to produce, for example, ethylene based homopolymers and copolymers having HLMI values of greater than 30 g/10 min.

Aqueous methods for titanating a chromium/silica catalyst with an alkali metal

Methods for controlling the long chain branch content of ethylene homopolymers and copolymers produced in a polymerization process include the steps of contacting a metallocene compound, an organoaluminum compound, a high LCB activator-support, and a low LCB activator-support to form a catalyst composition, contacting the catalyst composition with ethylene and an optional olefin comonomer in a polymerization reactor system under polymerization conditions to produce an ethylene polymer having a LCB content, and controlling the relative amount of the high LCB activator-support and the low LCB activator-support in the catalyst composition to adjust the LCB content of the ethylene polymer.

Controlling long-chain branch content with dual activator-supports

Processes for converting methane into methanol are disclosed in which methane, water, and a supported chromium (VI) catalyst are contacted with a light beam at a wavelength in the UV-visible spectrum in an oxidizing atmosphere in a single reactor to form a reaction product comprising methanol, followed by discharging a reactor effluent containing the reaction product from the single reactor, and then separating methanol from the reaction product. Processes to produce methanol using additional reactors also are described, as well as related methanol production systems.

Methanol production from methane utilizing a supported chromium catalyst

Methods for making a supported chromium catalyst are disclosed, and can comprise contacting a silica-coated alumina containing at least 30 wt. % silica with a chromium-containing compound in a liquid, drying, and calcining in an oxidizing atmosphere at a peak temperature of at least 650° C. to form the supported chromium catalyst. The supported chromium catalyst can contain from 0.01 to 20 wt. % chromium, and typically can have a pore volume from 0.5 to 2 mL/g and a BET surface area from 275 to 550 m/g. The supported chromium catalyst subsequently can be used to polymerize olefins to produce, for example, ethylene-based homopolymers and copolymers having high molecular weights and broad molecular weight distributions.

Methods for making supported chromium catalysts with increased polymerization activity

Sulfated bentonite compositions are characterized by a total pore volume from 0.4 to 1 mL/g, a total BET surface area from 200 to 400 m/g, and an average pore diameter from 55 to 100 Angstroms. The sulfated bentonite compositions also can be characterized by a d50 average particle size in a range from 15 to 50 μm and a ratio of d90/d10 from 3 to 15. The sulfated bentonite compositions can contain a sulfated bentonite and from 10 to 90 wt. % of colloidal particles, or the sulfated bentonite compositions can contain a sulfated bentonite and from 0.2 to 10 mmol/g of zinc and/or phosphorus. These compositions can be utilized in metallocene catalyst systems to produce ethylene based polymers.

Modifications of sulfated bentonites and uses thereof in metallocene catalyst systems for olefin polymerization

Pyrolysis processes comprise contacting a waste polyolefin with a solid catalyst at a pyrolysis temperature to form a pyrolysis product containing C-Chydrocarbons. In some instances, the solid catalyst can be a silica-coated alumina, a fluorided silica-coated alumina, or a sulfated alumina, while in other instances, the solid catalyst can be any suitable solid oxide or chemically-treated solid oxide that is characterized by a d50 average particle size from 5 to 12 μm and a particle size span from 0.7 to 1.7. Hydrocarbon compositions are formed from the pyrolysis of waste polyolefins with specific amounts of methane and higher carbon number hydrocarbons.

Solid oxide and chemically-treated solid oxide catalysts for the pyrolysis of polyethylene

Fluorided silica-coated alumina activator-supports have a bulk density from 0.15 to 0.37 g/mL, a total pore volume from 0.85 to 2 mL/g, a BET surface area from 200 to 500 m/g, an average pore diameter from 10 to 25 nm, and from 80 to 99% of pore volume in pores with diameters of greater than 6 nm. Methods of making the fluorided silica-coated alumina activator-supports and using the fluorided silica-coated aluminas in catalyst compositions and olefin polymerization processes also are described. Representative ethylene-based polymers produced using the compositions and processes have a melt index of 0.1 to 10 g/10 min and a density of 0.91 to 0.96 g/cm, and contain from 70 to 270 ppm solid oxide and from 2 to 18 ppm fluorine.

High porosity fluorided silica-coated alumina activator-supports and uses thereof in metallocene-based catalyst systems for olefin polymerization

Supported chromium (VI) catalysts containing a solid oxide, 0.05 to 5 wt. % chromium, and 0.2 to 20 wt. % carbon, in which the solid oxide or the catalyst has a particle size span from 0.5 to 1.4, less than 3 wt. % has a particle size greater than 100 μm, and less than 10 wt. % has a particle size less than 10 μm, can be contacted with an olefin monomer in a fluidized bed reactor or other suitable polymerization reactor to produce an olefin polymer. Representative ethylene-based polymers produced using the chromium catalysts have a HLMI of 4 to 70 g/10 min, a density from 0.93 to 0.96 g/cm, from 150 to 680 ppm solid oxide (such as silica), from 0.5 to 3 ppm chromium, and a film gel count of less than 15 catalyst particle gels per ftof 25 micron thick film and/or a gel count of less than or equal to 50 catalyst particles of greater than 100 μm (in diameter) per five grams of the ethylene polymer.

Particle size control of silyl chromate catalysts and uses thereof in fluidized bed reactors

Processes for converting a hydrocarbon reactant into an alcohol compound and/or a carbonyl compound are disclosed in which the hydrocarbon reactant and a supported transition metal catalyst—containing molybdenum, tungsten, or vanadium—are irradiated with a light beam at a wavelength in the UV-visible spectrum, optionally in an oxidizing atmosphere, to form a reduced transition metal catalyst, followed by hydrolyzing the reduced transition metal catalyst to form a reaction product containing the alcohol compound and/or the carbonyl compound.

Transition metal-catalyzed production of alcohol and carbonyl compounds from hydrocarbons

Methods for making titanated silica supports, titanated chromium/silica pre-catalysts, and activated titanated chromium/silica catalysts are disclosed in which hydrogen peroxide and an alkali metal precursor are used during catalyst preparation. Resulting titanated chromium/silica pre-catalysts often contain silica, 0.1 to 5 wt. % chromium, 0.1 to 10 wt. % titanium, and less than or equal to 4 wt. % carbon, and further contain an alkali metal or zinc at a molar ratio of alkali metal:titanium or zinc:titanium from 0.02:1 to 3:1 and/or at an amount in a range from 0.01 to 2 mmol of alkali metal or zinc per gram of the silica. High melt index potential activated titanated chromium/silica catalysts can be used to polymerize olefins to produce, for example, ethylene based homopolymers and copolymers having HLMI values of greater than 30 g/10 min.

Disclosed herein are methods for preparing fluorided solid oxides by contacting an acidic fluorine-containing compound with an inorganic base to form an aqueous mixture having a pH of at least 4, followed by contacting a solid oxide with the aqueous mixture to produce the fluorided solid oxide. Also disclosed are methods for preparing fluorided solid oxides by contacting an acidic fluorine-containing compound with a solid oxide to produce a mixture, followed by contacting the mixture with a inorganic base to produce the fluorided solid oxide at a pH of at least about 4. The fluorided solid oxide can be used as an activator component in a catalyst system for the polymerization of olefins.

Processes for producing fluorided solid oxides and uses thereof in metallocene-based catalyst systems

Disclosed herein are ethylene-based polymers generally characterized by a melt index of less than 15 g/10 min, a density from 0.91 to 0.945 g/cm, a CY-a parameter at 190° C. from 0.2 to 0.6, an average number of long chain branches per 1,000,000 total carbon atoms of the polymer in a molecular weight range of 500,000 to 2,000,000 g/mol of less than 5, and a maximum ratio of η/3η at an extensional rate of 0.03 secin a range from 3 to 15. The ethylene polymers have substantially no long chain branching in the high molecular weight fraction of the polymer, but instead have significant long chain branching in the lower molecular weight fraction, such that polymer melt strength and bubble stability are maintained for the fabrication of blown films and other articles of manufacture. These ethylene polymers can be produced using a dual catalyst system containing a single atom bridged metallocene compound with an indenyl group and a cyclopentadienyl group, and an unbridged hafnium metallocene compound with two cyclopentadienyl groups.

Dual catalyst system for producing LLDPE and MDPE copolymers with long chain branching for film applications

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Bartlesville, OK, United States of America

Max P McDaniel