Exxonmobil Research and Engineering Company

Exxonmobil Chemical Patents Inc.

Exxonmobil Technology and Engineering Company

Michael P Lanci

Changyub Paek

Javier Guzman

Catherine M Dorsi

Jihad Mohammed Dakka

Stuart Leon Soled

Sabato Miseo

Randall David Partridge

Joseph Ernest Baumgartner

Thomas Elmer Green

Stephen Zushma

Allen Wayne Burton

Lei Zhang

Bryan A Patel

Michael Salciccioli

Gary Paul Schleicher

Christine Esther Kliewer

Benjamin A McCool

Victor DeFlorio

Michael W Weber

Carla S Pereira

Tracie L Owens

Kanmi Mao

Joshua W Allen

J Scott Buchanan

Paolo Andres Cuello Penaloza

Nathaniel M Eagan

Lukasz Koziol

Jarid M Metz

Scott Jeffrey Weigel

Peter I Ravikovitch

Xiaochun Xu

Lorenzo C DeCaul

George W Huber

Sumathy Raman

Peter Galebach

Monica D Lotz

Lorenzo Cophard DeCaul

Wei Tang

Ashley M Wittrig

Constantinos P Bokis

Wenzhao Wu

Provided are two-stage processes by which primary alcohols such as ethanol or 1-butanol are converted into distillate-range ethers and olefins utilizing Guerbet coupling followed by intermolecular dehydration. The ethers can be used, for example, as cetane-improvers in diesel fuel, while the olefins can be hydrogenated to afford paraffins.

Processes for producing ethers and olefins from primary alcohols

Processes for producing alcohols from biomass are provided. The processes utilize supercritical methanol to depolymerize biomass with subsequent conversion to a mixture of alcohols. In particular the disclosure relates to continuous processes which produce high yields of alcohols through recycling gases and further employ dual reactor configurations which improve overall alcohol yields. Processes for producing higher ethers and olefins from the so-formed alcohols, through alcohol coupling and subsequent dehydration are also provided. The resulting distillate range ethers and olefins are useful as components in liquid fuels, such as diesel and jet fuel.

Processes for producing alcohols from biomass and further products derived therefrom

Processes are described for separating 3,4'- and 4,4&#x2032;-dimethylbiphenyl from a mixture comprising at least 3,3&#x2032;-, 3,4&#x2032;- and 4,4&#x2032;-dimethylbiphenyl. In the processes, the mixture is cooled to produce a crystallization product comprising at least of the 4,4&#x2032;-dimethylbiphenyl from the feed mixture and a first mother liquor product. The first mother liquor product is distilled to produce a bottoms stream enriched in 4,4&#x2032;-dimethylbiphenyl as compared with the first mother liquor product and an overhead stream deficient in 4,4&#x2032;-dimethylbiphenyl as compared with the first mother liquor product. The overhead stream is then cooled to produce a second crystallization product comprising at least part of the 3,4&#x2032;-dimethylbiphenyl from the overhead stream and a second mother liquor product.

Production and use of 3,4' and 4,4&#x2032;-dimethylbiphenyl isomers

In a process for producing a methyl-substituted biphenyl compound, at least one methyl-substituted cyclohexylbenzene compound of the formula: wherein each of m and n is independently 1, 2, or 3, is contacted with hydrogen in the presence of a hydrogenation catalyst to produce a hydrogenation reaction product comprising at least one methyl-substituted bicyclohexane compound, and the methyl-substituted bicyclohexane compound is then contacted with a dehydrogenation catalyst to produce a dehydrogenation reaction product comprising at least one methyl-substituted biphenyl compound.

Production of methyl-substituted biphenyl compounds

In a process for separating dimethyl biphenyl isomers a mixture comprising one or more 3,3', 3,4&#x2032;- or 4,4&#x2032;-dimethyl biphenyl isomers, one or more 2,X&#x2032;-dimethyl biphenyl isomers (where X=2, 3, or 4) and one or more further hydrocarbon components is contacted with a first adsorbent, thereby selectively adsorbing one or more of the dimethyl biphenyl isomers within the first adsorbent. A first raffinate stream containing less selectively adsorbed components is withdrawn from the first adsorbent and a first extract stream containing selectively adsorbed dimethyl biphenyl isomers is withdraw. The selectively adsorbed dimethyl biphenyl isomers comprise one or more of 3,3&#x2032;-, 3,4&#x2032;- or 4,4&#x2032;-dimethyl biphenyl isomers and one or more of 2,X&#x2032;-dimethyl biphenyl isomers (where X&#x2032;=2, 3, or 4).

Production and separation of dimethyl biphenyl isomers

In a process for producing one or more 2,X'-dimethyl biphenyl isomers (where X=2, 3 or 4), a feed comprising toluene is contacted with hydrogen in the presence of a hydroalkylation catalyst under conditions effective to produce a hydroalkylation reaction product comprising (methylcyclohexyl)toluene. At least part of the hydroalkylation reaction product is dehydrogenated in the presence of a dehydrogenation catalyst under conditions effective to produce a dehydrogenation reaction product comprising dimethyl biphenyl isomers. The dehydrogenation reaction product is then separated into at least a first stream comprising one or more 3,3&#x2032;-, 3,4&#x2032;- and 4,4&#x2032;-dimethyl biphenyl isomers and at least one second stream comprising one or more 2,X&#x2032;-dimethyl biphenyl isomers (where X=2, 3 or 4). The at least one second stream is then contacted with a first adsorbent thereby selectively adsorbing one or more 2,X&#x2032;-dimethyl biphenyl isomers (where X=2, 3 or 4) within said first adsorbent and then withdrawing from said first adsorbent a first extract stream comprising one or more selectively adsorbed 2,X&#x2032;-dimethyl biphenyl isomers (where X=2, 3 or 4) and a first raffinate stream comprising one or more less selectively adsorbed components.

In a process for separating one or more 3,3'-, 3,4&#x2032;- and 4,4&#x2032;-dimethyl biphenyl isomers, a feed comprising the isomers is contacted with a zeolite adsorbent which contains one or more metal cations in the +1 or +2 oxidation states. Separation processes for each of the 3,3&#x2032;-, 3,4&#x2032;- and 4,4&#x2032;-dimethyl biphenyl isomers is provided.

Processes for separating dimethyl biphenyl isomers using zeolite adsorbents

A process for separating dimethyl biphenyl (DMBP) isomers, including contacting a mixture of 3,3'-DMBP, 3,4&#x2032;-DMBP and 4,4&#x2032;-DMBP in a first solvent with a 12-member ring zeolite exchanged with potassium or barium, or combinations thereof, and adsorbing the 3,3&#x2032;-DMBP onto the 12-member ring zeolite, such as by passing the mixture through at least one packed bed of the potassium and/or barium exchanged 12-member ring zeolite.

Adsorptive separation of dimethyl biphenyl regioisomers using 12-member ring zeolite sorbents

A process for selective oxidation of dimethyl-1,1'-biphenyl to form methyl-1,1&#x2032;-biphenyl mono-carboxylic acid(s), comprising contacting a solution of dimethyl-1,1&#x2032;-biphenyl in acetic acid solvent in the presence of a Co(II) acetate catalyst and air, and optionally adding a co-solvent, or adding sodium or potassium acetate, and oxidizing the dimethyl-1,1&#x2032;-biphenyl under time and temperature conditions sufficient to form one or more methyl-1,1&#x2032;-biphenyl mono-carboxylic acid(s). The mono-carboxylic acids are advantageously isolated and esterified to form biphenyl mono-esters for use as plasticizers.

Selective aerobic oxidation of dimethylbiphenyls

A process for selective oxidation of dimethyl-1,1'-biphenyl(s) to form methyl-1,1&#x2032;-biphenyl mono-carboxylic acid(s), which can be esterified to form plasticizers, comprising contacting a solution of dimethyl-1,1&#x2032;-biphenyl(s) in acetic acid in the presence of an oxidation catalyst and air under time and temperature conditions sufficient to oxidize the dimethyl-1,1&#x2032;-biphenyl(s) into one or more methyl-1,1&#x2032;-biphenyl mono-carboxylic acid(s) products, conducting at least one of (i) adding an antisolvent, or (ii) optimizing a total conversion of dimethyl-1,1&#x2032;-biphenyl(s) by oxidation based upon a molar ratio of dimethyl-1,1&#x2032;-biphenyl isomers, or (iii) precipitating the methyl-1,1&#x2032;-biphenyl mono-carboxylic acid(s) products by lowering the temperature, or (iv) decreasing the oxidation reaction temperature to enhance conversion of aldehydes over methyl functional groups, so as to limit over-oxidation of the dimethyl-1,1&#x2032;-biphenyl(s), wherein the oxidation reaction is conducted in the absence of bromide-containing catalysts.

Methods are provided for modifying hydrogenation catalysts having silica supports (or other non-alumina supports) with additional alumina, and using such catalysts to achieve unexpectedly superior hydrogenation of feedstocks. The modified hydrogenation catalysts can have a relatively low cracking activity while providing an increased activity for hydrogenation.

Method and system for producing low aromatic hydrocarbon products

Noble metal hydrogenation catalysts and aromatic saturation methods

In a process for producing one or more 3,3'-, 3,4&#x2032;- and 4,4&#x2032;-dimethyl biphenyl isomers, a feed comprising toluene is contacted with hydrogen in the presence of a hydroalkylation catalyst under conditions effective to produce a hydroalkylation reaction product comprising (methylcyclohexyl)toluenes. At least part of the hydroalkylation reaction product is dehydrogenated in the presence of a dehydrogenation catalyst under conditions effective to produce a dehydrogenation reaction product comprising a mixture of dimethyl biphenyl isomers. The dehydrogenation reaction product is then separated into at least a first stream containing one or more 3,3&#x2032;-, 3,4&#x2032;- and 4,4&#x2032;-dimethyl biphenyl isomers and at least one second stream comprising one or more 2,X&#x2032;-dimethyl biphenyl isomers (where X is 2, 3, or 4). The 3,3&#x2032;-, 3,4&#x2032;- and 4,4&#x2032;-dimethyl biphenyl isomers are then separated utilizing selective adsorption.

Production and separation of 3,3'-, 3,4&#x2032;- and 4,4&#x2032;-dimethyl biphenyl isomers

In a process for separating one or more 3,3'-, 3,4&#x2032;- and 4,4&#x2032;-dimethyl biphenyl isomers, a feed comprising the isomers is contacted with an adsorbent containing a zeolite having a largest diffuse along dimension of at least 4 Angstroms. The adsorbents provide selective adsorption of 4,4&#x2032;-dimethyl biphenyl.

Noble metal hydrogenation catalysts with low cracking activity

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Flemington, NJ, United States of America

Michael P Lanci