Chevron Phillips Chemical Company LP

Chevron Philips Chemical Company, LP

Alan L Solenberger

Max P McDaniel

Eric D Schwerdtfeger

Ted H Cymbaluk

Kathy S Clear

Qing R Yang

Jeremy M Praetorius

Errun Ding

Rex E Murray

Gary L Glass

William B Beaulieu

Connor D Boxell

Steve J Secora

Youlu Yu

Kathy S Collins

Albert P Masino

Kumudini Jayaratne

Max P Mcdaniel

Jared L Barr

Christopher E Wittner

Anand Ramanathan

Micheal P Stevens

Zachary T Kilpatrick

Andrew T Blagg

Steven J Secora

Conner D Boxell

Qing Yang

Kumudini C Jayaratne

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 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.

A method comprising a) drying a support material comprising silica at temperature in the range of from about 150&#xb0; C. to about 220&#xb0; C. to form a dried support; b) contacting the dried support with methanol to form a slurried support; c) subsequent to b), cooling the slurried support to a temperature of less than about 60&#xb0; C. to form a cooled slurried support; d) subsequent to c), contacting the cooled slurried support with a titanium alkoxide to form a titanated support; and e) thermally treating the titanated support by heating to a temperature of equal to or greater than about 150&#xb0; C. for a time period of from about 5 hours to about 30 hours to remove the methanol and yield a dried titanated support.

Methods of preparing a catalyst

A polymer having a long chain branching content peaking at greater than about 20 long chain branches per million carbon atoms, and a polydispersity index of greater than about 10 wherein the long chain branching decreases to approximately zero at the higher molecular weight portion of the molecular weight distribution. A polymer having a long chain branching content peaking at greater than about 8 long chain branches per million carbon atoms, a polydispersity index of greater than about 20 wherein the long chain branching decreases to approximately zero at the higher molecular weight portion of the molecular weight distribution. A polymer having a long chain branching content peaking at greater than about 1 long chain branches per chain, and a polydispersity index of greater than about 10 wherein the long chain branching decreases to approximately zero at the higher molecular weight portion of the molecular weight distribution.

Long chain branched polymers and methods of making same

A method comprising calcining a catalyst precursor comprising chromium and a silica support material at a temperature in the range of from about 95&#xb0; C. to about 400&#xb0; C. in a bed fluidized by a gas flowing at a volumetric flow rate of from about 2.5 to about 30 times the settled volume of the bed per minute to form a calcined catalyst precursor. A method comprising calcining a catalyst precursor comprising chromium and silica at a temperature in the range of from about 95&#xb0; C. to about 400&#xb0; C. with a gas flowing through the bed at a gas hourly space velocity of from about 15 to about 200 per hour. A method comprising calcining a catalyst precursor comprising chromium and silica at a temperature in the range of from about 95&#xb0; C. to about 400&#xb0; C. with a gas flowing through the bed at a weight hourly space velocity of from about 1.9 to about 240 per hour.

A method of preparing a catalyst comprising a) contacting (i) a silica-support, (ii) an oxotitanium compound, (iii) a chromium-containing compound, and (iv) an optional solvent to form a first aqueous mixture comprising a pre-catalyst and a reaction media having from about 1 wt. % to about 99 wt. % water; b) thermally treating the pre-catalyst by heating to a temperature of from about 400&#xb0; C. to about 1000&#xb0; C. for a time period of from about 1 minute to about 24 hours to form the catalyst. A method of preparing a catalyst comprising contacting a hydrated support material comprising silica with a chromium-containing compound to form a first aqueous mixture comprising a chrominated support; contacting the first aqueous mixture comprising a chrominated support with a solution comprising (i) a solvent and (ii) an oxotitanium compound to form a second aqueous mixture comprising a pre-catalyst; and thermally treating the pre-catalyst to form the catalyst.

A method comprising a) calcining a silica support at temperature in the range of from about 100&#xb0; C. to about 500&#xb0; C. to form a precalcined silica support; b) contacting the precalcined silica support with a titanium alkoxide to form a titanated support; c) subsequent to b), contacting the titanated support with a polyol to form a polyol associated titanated support (PATS); d) contacting at least one of the silica support, pre-calcined silica support, the titanated support, the PATS, or combinations thereof with a chromium-containing compound to form a polymerization catalyst precursor; e) drying the polymerization catalyst precursor to form a dried polymerization catalyst precursor; and f) calcining the dried polymerization catalyst precursor to produce a polymerization catalyst, wherein less than about 0.1 wt. % of a highly reactive volatile organic compound (HRVOC) is emitted during the calcining of the dried polymerization catalyst precursor.

A method comprising contacting a support material with a transition metal compound to produce a mixture; thermally treating the mixture in the presence of oxygen at a temperature in a range of from about 100&#xb0; C. to about 500&#xb0; C. for a period of from about 1 hour to about 10 hours, wherein at least a portion of the transition metal sublimes onto the support material to produce a support material comprising a dispersed transition metal; and thermally treating the support material comprising the dispersed transition metal in an oxidizing atmosphere at a temperature in a range of from about 550&#xb0; C. to about 900&#xb0; C. for a period of from about 1 hour to about 10 hours to produce a polymerization catalyst.

Polymerization catalysts and polymers

The present invention provides dual catalyst systems and polymerization processes employing these dual catalyst systems. The disclosed polymerization processes can produce olefin polymers at higher production rates, and these olefin polymers may have a higher molecular weight and/or a lower melt index.

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Bartlesville, OK, United States of America

Alan L Solenberger