Chevron Phillips Chemical Company LP

Other

Pasquale Iacono

Mark L Hlavinka

Max P McDaniel

Gregory G Hendrickson

Graham R Lief

Eric J Haschke

Carlton Edwin Ash

Jamie N Sutherland

Anand Ramanathan

Catalysts and catalytic processes for the synthesis of acrylic acid and other α,β-unsaturated carboxylic acids and their salts, which are carried out in a diluent or in the absence of a diluent. In an aspect, ethylene and COcan be contacted with a Group 8-11 transition metal precursor compound or a Group 8-11 transition metal metalalactone compound in the presence of a metal-treated chemically-modified solid oxide (MT-CMSO) or a metal-treated solid oxide (MT-SO), to form a metal acrylate. As the catalytic activity wanes in either the presence or absence of a diluent, pressure cycling—that is, pressurizing the reaction system with COand an olefin such as ethylene for a time period, releasing the pressure, then re-pressurizing with COand ethylene—can rejuvenate the catalyst and restore its declining catalytic activity.

Gas phase process for acrylate production from ethylene and carbon dioxide

This disclosure provides processes for forming acrylic acid and other &#x3b1;,&#x3b2;-unsaturated carboxylic acids and their salts, including catalytic processes, and catalyst systems for effecting the processes. For example, there is provided a catalyst system for producing an &#x3b1;,&#x3b2;-unsaturated carboxylic acid or a salt thereof, the catalyst system comprising: (a) a transition metal precursor compound comprising a Group 8-11 transition metal and at least one first ligand; (b) optionally, at least one second ligand; and (c) an anionic polyaromatic resin with associated metal cations. The catalyst system can further comprise (d) an olefin; (e) carbon dioxide (CO); and (f) a diluent. Methods of regenerating the anionic polyaromatic resin with associated metal cations are described.

Formation of &#x3b1;,&#x3b2;-unsaturated carboxylic acids and salts thereof from metalalactones and anionic polyelectrolytes

This disclosure provides for catalyst systems and processes for forming an &#x3b1;,&#x3b2;-unsaturated carboxylic acid or a salt thereof. In an aspect, the catalyst system can comprise: a transition metal precursor comprising a Group 8-11 transition metal and at least one first ligand; optionally, at least one second ligand; an olefin; carbon dioxide (CO); a diluent; and an oxoacid anion-substituted polyaromatic resin comprising a sulfonated polyaromatic resin, a phosphonated polyaromatic resin, a sulfinated polyaromatic resin, a thiosulfonated, or a thiosulfinated polyaromatic resin, and further comprising associated metal cations. Methods of regenerating the polyaromatic resin with associated metal cations are described.

Sulfur oxoacid-substituted and phosphorus oxoacid-substituted polyaromatic resins and salts thereof as promoters in acrylate production from coupling reactions of olefins and carbon dioxide

This disclosure provides for routes of synthesis of acrylic acid and other &#x3b1;,&#x3b2;-unsaturated carboxylic acids and their salts, including catalytic methods. For example, there is provided a process for producing an &#x3b1;,&#x3b2;-unsaturated carboxylic acid or a salt thereof, the process comprising: (1) contacting in any order, a group 8-11 transition metal precursor, an olefin, carbon dioxide, a diluent, and a metal-treated chemically-modified solid oxide such as a sulfur oxoacid anion-modified solid oxide, a phosphorus oxoacid anion-modified solid oxide, or a halide ion-modified solid oxide, to provide a reaction mixture; and (2) applying reaction conditions to the reaction mixture suitable to produce the &#x3b1;,&#x3b2;-unsaturated carboxylic acid or the salt thereof. Methods of regenerating the metal-treated chemically-modified solid oxide are described.

Effects of catalyst concentration and solid activator on nickel-mediated olefin/carbon dioxide coupling to acrylates

Disclosed is a continuous process for producing &#x3b1;,&#x3b2;-unsaturated carboxylic acids or salts thereof, comprising: 1) in a first stage, contacting (a) a transition metal precursor compound comprising at least one first ligand, (b) optionally, at least one second ligand, (c) an olefin, (d) carbon dioxide (CO), and (e) a diluent to form a first composition; 2) in a second stage, contacting a polyanionic solid with the first composition to form a second composition; and 3) in a third stage, (a) contacting the second composition with a polar solvent to release a metal salt of an &#x3b1;,&#x3b2;-unsaturated carboxylic acid and form a reacted solid. Methods of regenerating the polyanionic solid are described.

Continuous process for the conversion of olefins and carbon dioxide to acrylates via solution phase reactor

This disclosure provides routes of synthesis of acrylic acid and other &#x3b1;,&#x3b2;-unsaturated carboxylic acids and their salts, including catalytic methods. In an aspect, there is provided a process for producing an &#x3b1;,&#x3b2;-unsaturated carboxylic acid or a salt thereof, the process comprising: (1) contacting in any order a group 8-11 transition metal precursor compound comprising at least one first ligand, at least one second ligand, an olefin, carbon dioxide, a diluent, and an anionic polyaromatic resin with associated metal cations to provide a reaction mixture; and (2) applying conditions to the reaction mixture suitable to produce the &#x3b1;,&#x3b2;-unsaturated carboxylic acid or a salt thereof. Methods of regenerating the polyaromatic resin with associated metal cations are described.

Formation of alpha,beta-unsaturated carboxylic acids and salts thereof from metalalactones and anionic polyelectrolytes

The present invention discloses processes for oligomerizing an olefin feedstock containing Cto Calpha olefins using a catalyst system containing a metallocene compound, an organoaluminum compound, and a suspension of a chemically-treated solid oxide. The liquid medium for the suspension of the chemically-treated solid oxide can be an alpha-olefin oligomer product formed by the oligomerization process.

Methods for the preparation and use of suspensions of chemically-treated solid oxides in an olefin-derived liquid medium

Processes for producing an &#x3b1;,&#x3b2;-unsaturated carboxylic acid, such as acrylic acid, or a salt thereof, using treated solid oxides are disclosed. The treated solid oxides can be calcined solid oxides, metal-treated solid oxides, or metal-treated chemically-modified solid oxides, illustrative examples of which can include sodium-treated alumina, calcium-treated alumina, zinc-treated alumina, sodium-treated sulfated alumina, sodium-treated fluorided silica-coated alumina, and similar materials.

Methods for the production of &#x3b1;,&#x3b2;-unsaturated carboxylic acids and salts thereof

This disclosure provides for routes of synthesis of &#x3b1;,&#x3b2;-unsaturated carboxylic acids and their salts, including acrylic acid. For example, disclosed is a process for producing an &#x3b1;,&#x3b2;-unsaturated carboxylic acid or its salt, comprising: (1) contacting a group 8-11 transition metal precursor, an olefin, carbon dioxide, a diluent, and a sulfur oxoacid anion-substituted polyaromatic resin or a phosphorus oxoacid anion-substituted polyaromatic resin with associated metal cations to provide a mixture; and (2) applying reaction conditions to the mixture suitable to produce the &#x3b1;,&#x3b2;-unsaturated carboxylic acid or a salt thereof. Methods of regenerating the polyaromatic resin with associated metal cations are described.

This disclosure provides for routes of synthesis of acrylic acid and other &#x3b1;,&#x3b2;-unsaturated carboxylic acids and their salts, including catalytic methods. For example, there is provided a process for producing an &#x3b1;,&#x3b2;-unsaturated carboxylic acid or a salt thereof, the process comprising: (1) contacting in any order, a group 8-11 transition metal precursor, an olefin, carbon dioxide, a diluent, and a polyaromatic resin with associated metal cations to provide a reaction mixture; and (2) applying conditions to the reaction mixture suitable to produce the &#x3b1;,&#x3b2;-unsaturated carboxylic acid or a salt thereof. Methods of regenerating the polyaromatic resin with associated metal cations are described.

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Bartlesville, OK, United States of America

Pasquale Iacono