Uop Lcc

Allied Corporation

Thomas P Malloy

Dusan J Engel

Mark A Halter

Raymond John Swedo

Laszlo T Nemeth

David W House

Jennifer S Holmgren

Timothy A Brandvold

Chwu-Ching Jan

George W Lester

Michael D Tufano

Richard R Jones

Bipin Virpal Vora

Russell W Johnson

Lee Hilfman

Ronald P Rohrbach

Peter K Nickl

Mary J Maliarik

James P Shoffner

Stephen A Munk

Louis J DeFilippi

Roy C Berg

Eric M Hyatt

Steven R Paeschke

A process of effecting an acid catalyzed reaction wherein a reactant capable of undergoing an acid catalyzed reaction is contacted with an acid functionalized organically-bridged polysilsesquioxane catalyst where all of the acid functionality is covalently bonded to the organic portion of an organically-bridged polysilsesquioxane framework has been developed. The acid functionalized organically-bridged polysilsesquioxane is formed by polymerizing a monomer through sol-gel processing to form an organically-bridged polysilsesquioxane, reacting an acid group onto the organic portion of the organically-bridged polysilsesquioxane, and recovering the acid functionalized product. An embodiment of the invention is where the acid catalyzed reaction is the hydration of olefins, alkylation, acylation, isomerization, or aldol condensation/elimination. A specific embodiment of the invention is effecting the aldol condensation/elimination reaction of acetone with itself to form mesityl oxide by contacting the acetone with an effective amount of sulfonated phenylene-bridged polysilsesquioxane.

Acid functionalized organically-bridged polysilsesquioxanes as catalysts

The oxidation of olefinic compounds generally using hydroperoxides, especially aqueous solutions of hydrogen peroxide, can be effected in high yield and with good selectivity in the presence of a catalyst which is a mixture of small particles of titania and a titanosilicalite. Small particle size is essential in affording a catalyst with good activity and selectivity, with particle sizes no more than about 0.3 microns being the preferred mode of operation. Dilute aqueous hydrogen peroxide solutions may be used with good results. The resulting epoxidation, even when carried out at modest temperatures and with dilute aqueous hydrogen peroxide solutions, afford superior results in epoxidation relative to TS-1.

Titanosilicate as an epoxidation catalyst for olefins

A process for forming a solid acid catalyst where all of the add functionality is covalently bonded to the organic portion of an organically-bridged polysilsesquioxane framework has been developed. The process involves polymerizing a monomer through sol-gel processing to form an organically-bridged polysilsesquioxane, reacting an acid group onto the organic portion of the organically-bridged polysilsesquioxane, and recovering the acid functionalized product. The invention also includes the product acid functionalized organically-bridged polysilsesquioxane catalyst of the process described. The catalyst is unique in that the acid functionality is incorporated within an organic-inorganic hybrid framework as opposed to being attached to pendant organic groups.

Process for forming acid functionalized organically-bridged

The oxidation of olefinic compounds generally using hydroperoxides, especially aqueous solutions of hydrogen peroxide, can be effected in high yield and with good selectivity in the presence of a titania-supported titanosilicate catalyst. Dilute aqueous hydrogen peroxide solutions may be used with good results. The resulting epoxidation, even when carried out at modest temperatures and with dilute aqueous hydrogen peroxide solutions, afford superior results in epoxidation relative to TS-1.

Epoxidation of olefins using a titania-supported titanosilicate

Base-catalyzed transesterification may be effected in the presence of certain metal oxide solid solutions and layered double hydroxides as the basic catalyst. Use of the latter materials as the base catalyst readily permits one to conduct transesterification in a continuous manner. Such a continuous process is applicable to esters generally and is not limited to any particular structural types of esters or alcohols. Transesterification of detergent range alkyl acetates by this method leads to the formation of the corresponding detergent range alcohols in excellent yield and with quite high selectivity.

Transesterification using metal oxide solid solutions as the basic

Nitro polyamines, and especially dinitro polyamines, can be readily reduced by a catalyst of zerovalent nickel on silica where the silica contains not more than 10% alumina and where the nickel content of the finished catalyst may be as high as 85%. The reductions can be performed under relatively low temperatures between 40.degree. and 120.degree. C. to avoid the problem of heat lability of the reactant nitro polyamines. Hydrogenations proceed with good conversion as well as good selectivity and the method offers a means of continuous hydrogenation of nitro polyamines.

Continuous reduction of a hindered nitro moiety in aliphatic nitro

Certain crystalline titanoaluminosilicate molecular sieve compositions having titanium, aluminum, and silicon present as framework tetrahedral oxide units are particularly effective in hydroxylating the aromatic nucleus of aromatic compounds using hydrogen peroxide, even where the hydrogen peroxide is used at concentrations of 10 weight percent or less. The variant where the exchangeable hydrogens of the titanoaluminosilicate are replaced by an alkali or alkaline earth metal cation is particularly favored because of the concomitant increase in selectivity. Excellent utilization of hydrogen peroxide often is observed, even when the hydroxylation is effected at temperatures under about 60.degree. C.

Oxidation of aromatics to hydroxyaromatics using aluminosilicates

This invention relates to a process for removing impurities contained in a teritary butyl alcohol feedstock. The process involves contacting the feedstock with an iron (II) compound such as iron (II) chloride, under an inert atmosphere at elevated pressures and temperatures for a time sufficient to reduce the peroxides to alcohols and oxidize the iron (II) to iron (III). The iron (II) compound is added in a homogeneous phase which, after reaction has occurred, gives a mixture of the treated teritary butyl alcohol, iron (III) compound and any residual iron (II) compound. The iron (III) and any iron (II) compounds are separated from the product by contacting the mixture with a cation exchange column.

Process for decomposing peroxide impurities in a teritary butyl alcohol

This invention relates to a process for removing peroxide impurities contained in a tertiary butyl alcohol feedstock. The process involves contacting the feedstock with an iron (II) compound such as iron (II) chloride, under an inert atmosphere at elevated pressures and temperatures for a time sufficient to reduce the peroxides to alcohols and oxidize the iron (II) to iron (III). The iron (II) compound may be added in a homogeneous phase or it may be deposited on a support. When the iron (II) is added as a homogeneous phase, it is separated from the product by contacting the mixture with a cation exchange column. Finally, when a supported iron (II) compound is used, the process may be run in a batch or continuous mode.

Process for decomposing peroxide impurities in a tertiary butyl alcohol

A diethyltoluene mixture rich in 2,5-diethyltoluene and containing less tha 5% of the 3,5-diethyltoluene can be prepared by methylating 1,4-diethylbenzene with an excess of methanol in the presence of amorphous silica-alumina catalysts. The most desirable catalysts have a silica:alumina ratio from about 2:1 through about 9:1. Methylation is conveniently effected in a temperature range between about 300.degree. C. and about 450.degree. C. and most desirably in a hydrogen atmosphere.

Preparation of 2,2-diethyltoluene

Fibers containing free amino groups, and especially polyamide fibers, can be made resistant to certain stains, especially those resulting from food grade dyes, by contacting the fiber with a solution of an aliphatic sulfonic acid containing 8 to 24 carbon atoms. Branched chain aliphatic sulfonic acids are more effective than the linear aliphatic sulfonic acids, and branching at the carbon bearing the sulfonic acid group is more effective than branching at any other carbon. Contacting the fiber with the solution of the aliphatic sulfonic acid needs to be done under acidic conditions, most preferably at a pH between 0.5 to 5.0.

Imparting stain resistance to certain fibers

Surface-modified electrodes which may be used in electrochemical cells for production of electrical energy comprise an enzyme immobilized on a support. The support consists of at least a monolayer coating of a carbonaceous pyropolymer possessing recurring units containing at least carbon and hydrogen atoms composited on a high surface area refractory inorganic oxide such that the carbonaceous pyropolymer monolayer coating replicates the surface area and macropore volume of the inorganic oxide. The coated support is then treated by impregnation with a water-soluble polyamine followed by contact with a solution of a molar excess of a bifunctional monomeric material to form a copolymer which provides pendant bonding sites. The copolymer is entrapped and adsorbed in the pores of the support material to provide a permanent attachment thereto. The treated support is then contacted with an excess of an enzyme to effect the conjugate attachment of the enzyme to the treated support. The immobilized enzyme will act as a working electrode in the presence of a predetermined substrate such as glucose to provide electrical energy.

Surface-modified electrodes

The recovery of residual oil which is found in subterranean reservoirs may be accomplished by utilizing an aqueous surfactant slug to reduce the interfacial tension between oil and water. An effective surfactant slug which may be used will comprise a mixture of: (1) from about 1 to about 10% of a sulfonate of a mixture of mono- and dialkyl-substituted aromatic hydrocarbon which has been obtained by the alkylation of an aromatic hydrocarbon with an olefinic hydrocarbon in the presence of a hydrogen fluoride catalyst; (2) a lower alkyl alcohol which possesses from about 3 to about 6 carbon atoms; and (3) a nonionic cosurfactant comprising an ethoxylated n-alcohol which possesses from about 12 to about 15 carbon atoms.

Enhanced oil recovery

A process is disclosed for producing a mixture of mono- and diallkylated aromatic hydrocarbons suitable for use as a detergent or as a surfactant in enhanced oil recovery processes. Two alkylation reaction stages are used in series, with a separate amount of an acyclic olefin being charged to each reaction stage. The effluent of the second alkylation reaction stage is separated by fractionation to form a mixture of mono- and dialkylated hydrocarbons. A portion of this mixture is recycled to the second alkylation reaction stage, with remainder being withdrawn as the product stream.

Production of dialkylated aromatics

The preparation of syrups which contain a high glucose or maltose content may be effected in a two-step process. In the first step, a feedstock such as starch which has been pretreated with alpha-amylase to adjust the dextrose equivalent is contacted with an enzyme such as amyloglucosidase or beta-amylase immobilized on a solid support. The contact time is adjusted by correlating the residence time and the liquid hourly space velocity so as to provide a conversion percentage of starch in the range of from about 50% to 85%, thus avoiding the formation of undesired conversion products. The partially hydrolyzed reaction mixture from the enzyme treatment is then passed through an ultrafiltration membrane whereby the permeate comprising the high glucose or maltose content is recovered, while the retentate is recycled for admixture with the partially hydrolyzed reaction mixture or for further treatment with the immobilized enzyme.

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Lake Zurich, IL, United States of America

Thomas P Malloy