Amoco Corporation

Bp Corporation North America Inc.

Bp Amoco Corporation

Standard Oil Company (Indiana)

Gary P Hagen

Michael J Spangler

Thomas G Smith

Deborah T Hung

David A Palmer

Cecelia A Radlowski

John M Weis

Gregory E Schmidt

Douglas E Fjare

Daniel B Pourreau

George Albert Huff

William H Gong

Patrick E McMahon

David F Tatterson

Ruth A Montag

Wen-Dong Chang

Monica Cristina Regalbuto

John G Schaffhausen

Thomas E Nemo

Andreas B Ernst

Lewis E Grimes

Owen H Bailey

Economical processes are disclosed for production of components for refinery blending of transportation fuels which are liquid at ambient conditions by selective oxygenation of refinery feedstocks comprising a mixture of organic compounds. The organic compounds are oxygenated in a liquid reaction medium with an oxidizing agent and heterogeneous oxygenation catalyst system which exhibits a capability to enhance the incorporation of oxygen into a mixture of liquid organic compounds to form a mixture comprising hydrocarbons, oxygenated organic compounds, water of reaction, and acidic co-products. The mixture is separated to recover at least a first organic liquid of low density and at least a portions of the catalyst metal, water of reaction and acidic co-products. Advantageously, the organic liquid is washed with an aqueous solution of sodium bicarbonate solution, or other soluble chemical base capable to neutralize and/or remove acidic co-products of oxidation, and recover oxygenated product.

Process for oxygenation of components for refinery blending of transportation fuels

A particularly useful process which includes the steps of providing a feedstream comprising methanol, a soluble condensation promoting component capable of activating a heterogeneous acidic catalyst and a source of formaldehyde formed by conversion of methanol in the presence of a catalyst comprising copper and zinc, and heating this feedstream with the heterogeneous acidic catalyst in a catalytic distillation column to convert methanol and formaldehyde present to methylal and higher polyoxymethylene dimethyl ethers and to separate the methylal from the higher polyoxymethylene dimethyl ethers is disclosed. Advantageously, methylal and higher polyoxymethylene dimethyl ethers are formed and separated in a catalytic distillation column. By including within the column a section containing an anion exchange resin, an essentially acid-free product is obtained. Products can be used directly as a blending component, or fractionated, as by further distillation, to provide more suitable components for blending into fuel.

Preparation of polyoxymethylene dimethyl ethers by acid-activated catalytic conversion of methanol with formaldehyde formed by dehydrogenation of methanol

A particularly useful process which includes the steps of providing a feedstream comprising providing a source of formaldehyde formed by conversion of dimethyl ether in the presence of a catalyst comprising tungsten oxide; and (i) heating the feedstream with the heterogeneous acidic catalyst in a catalytic distillation column to convert methanol and formaldehyde present to methylal and higher polyoxymethylene dimethyl ethers and to separate the methylal from the higher polyoxymethylene dimethyl ethers is disclosed, and/or (ii) contacting the source of formaldehyde and a predominately dimethyl ether feedstream with a heterogeneous, condensation promoting catalyst capable of hydrating dimethyl ether under conditions of reaction sufficient to form an effluent comprising water, methanol, formaldehyde, dimethyl ether, and polyoxymethylene dimethyl ethers is disclosed. Unreacted dimethyl ether is recovered from the effluent and recycled to the formation of polyoxymethylene dimethyl ethers. The resulting dimethyl ether-free liquid mixture is heated in the presence of an acidic catalyst to convert at least the methanol and formaldehyde present to polyoxymethylene dimethyl ethers. Advantageously, methylal and higher polyoxymethylene dimethyl ethers are formed and separated in a catalytic distillation column. By including in the column an anion exchange resin, an essentially acid-free product is obtained which can be used directly as a blending component, or fractionated, as by further distillation, to provide more suitable components for blending into diesel fuel.

Preparation of polyoxymethylene dimethyl ethers by catalytic conversion of formaldehyde formed by oxidation of dimethyl ether

Preparation of polyoxymethylene dialkane ethers, by catalytic conversion of formaldehyde formed by dehydrogenation of methanol or dimethyl ether

A particularly useful process which includes the steps of providing a feedstream comprising a soluble condensation promoting component capable of activating a heterogeneous acidic catalyst and a source of formaldehyde formed by conversion of dimethyl ether in the presence of a catalyst comprising silver as an essential catalyst component; and heating the feedstream with the heterogeneous acidic catalyst in a catalytic distillation column to convert methanol and formaldehyde present to methylal and higher polyoxymethylene dimethyl ethers and to separate the methylal from the higher polyoxymethylene dimethyl ethers is disclosed. Advantageously, methylal and higher polyoxymethylene dimethyl ethers are formed and separated in a catalytic distillation column. By including in the column an anion exchange resin, an essentially acid-free product is obtained which can be used directly as a blending component, or fractionated, as by further distillation, to provide more suitable components for blending into diesel fuel.

Preparation of polyoxymethylene dimethyl ethers by acid-activated catalytic conversion of methanol with formaldehyde formed by oxy-dehydrogenation of dimethyl ether

A particularly useful process which includes the steps of providing a source of formaldehyde formed by conversion of methanol in the presence of a catalyst comprising oxides of molybdenum as an essential catalyst component; and contacting the source of formaldehyde and a predominately dimethyl ether feedstream with a heterogeneous, condensation promoting catalyst capable of hydrating dimethyl ether under conditions of reaction sufficient to form an effluent comprising water, methanol, formaldehyde, dimethyl ether, and polyoxymethylene dimethyl ethers is disclosed. Unreacted dimethyl ether is recovered from the effluent and recycled to the formation of polyoxymethylene dimethyl ethers. The resulting dimethyl ether-free liquid mixture is heated in the presence of an acidic catalyst to convert at least the methanol and formaldehyde present to polyoxymethylene dimethyl ethers. Advantageously, methylal and higher polyoxymethylene dimethyl ethers are formed and separated in a catalytic distillation column. By including in the column an anion exchange resin, an essentially acid-free product is obtained which can be used directly as a blending component, or fractionated, as by further distillation, to provide more suitable components for blending into diesel fuel.

Preparation of polyoxymethylene dimethyl ethers by catalytic conversion

A particularly useful process which includes the steps of providing a source of formaldehyde formed by conversion of dimethyl ether in the presence of a catalyst comprising copper and zinc; and contacting the source of formaldehyde and a predominately dimethyl ether feedstream with a heterogeneous, condensation promoting catalyst capable of hydrating dimethyl ether under conditions of reaction sufficient to form an effluent comprising water, methanol, formaldehyde, dimethyl ether, and polyoxymethylene dimethyl ethers is disclosed. Unreacted dimethyl ether is recovered from the effluent and recycled to the formation of polyoxymethylene dimethyl ethers. The resulting dimethyl ether-free liquid mixture is heated in the presence of an acidic catalyst to convert at least the methanol and formaldehyde present to polyoxymethylene dimethyl ethers. Advantageously, methylal and higher polyoxymethylene dimethyl ethers are formed and separated in a catalytic distillation column. By including in the column an anion exchange resin, an essentially acid-free product is obtained which can be used directly as a blending component, or fractionated, as by further distillation, to provide more suitable components for blending into diesel fuel.

A particularly useful process which includes the steps of providing a source of formaldehyde formed by conversion of methanol in the presence of a catalyst comprising silver as an essential catalyst component; and contacting the source of formaldehyde and a predominately dimethyl ether feedstream with a heterogeneous, condensation promoting catalyst capable of hydrating dimethyl ether under conditions of reaction sufficient to form an effluent comprising water, methanol, formaldehyde, dimethyl ether, and polyoxymethylene dimethyl ethers is disclosed. Unreacted dimethyl ether is recovered from the effluent and recycled to the formation of polyoxymethylene dimethyl ethers. The resulting dimethyl ether-free liquid mixture is heated in the presence of an acidic catalyst to convert at least the methanol and formaldehyde present to polyoxymethylene dimethyl ethers. Advantageously, methylal and higher polyoxymethylene dimethyl ethers are formed and separated in a catalytic distillation column. By including in the column an anion exchange resin, an essentially acid-free product is obtained which can be used directly as a blending component, or fractionated, as by further distillation, to provide more suitable components for blending into diesel fuel.

A particularly useful process of contacting a feedstream containing dioxygen, carbon monoxide, ether, and alkanol which can be vaporized under conditions of reaction, with a blend of catalysts which are heterogeneous to the feedstream, under conditions of reaction sufficient to form a mixture containing at least one higher molecular weight oxygenated organic compound. In another aspect this invention relates to a blend of catalysts consisting of at least one molecular sieve, natural or synthetic, which has been found useful for hydrocarbon conversion reactions and a catalyst comprising a metal halide or a mixed metal halide supported on active carbon which is effective in catalyzing direct formation of organic carbonates.

Continuous catalytic process for preparation of organic carbonates

A particularly useful process which includes the steps of providing a source of formaldehyde formed by conversion of dimethyl ether in the presence of a catalyst comprising silver as an essential catalyst component; and contacting the source of formaldehyde and a predominately dimethyl ether feedstream with a heterogeneous, condensation promoting catalyst capable of hydrating dimethyl ether under conditions of reaction sufficient to form an effluent comprising water, methanol, formaldehyde, dimethyl ether, and polyoxymethylene dimethyl ethers is disclosed. Unreacted dimethyl ether is recovered from the effluent and recycled to the formation of polyoxymethylene dimethyl ethers. The resulting dimethyl ether-free liquid mixture is heated in the presence of an acidic catalyst to convert at least the methanol and formaldehyde present to polyoxymethylene dimethyl ethers. Advantageously, methylal and higher polyoxymethylene dimethyl ethers are formed and separated in a catalytic distillation column. By including in the column an anion exchange resin, an essentially acid-free product is obtained which can be used directly as a blending component, or fractionated, as by further distillation, to provide more suitable components for blending into diesel fuel.

A continuous vapor phase processes for direct condensation of methanol and/or dimethyl ether with dilute acetylene feedstream to a mixture containing at least one higher molecular weight alkanol, such as n-propanol or isobutanol, over an alkaline catalyst which is, advantageously, an essentially magnesium oxide catalyst.

Continuous vapor phase process for direct conversion of methanol to

A continuous process for recovery of acetylene-free gaseous mixture from gaseous feedstreams containing acetylene and optionally other low molecular weight hydrocarbons by contacting the acetylene-containing feedstream with an alkanol in combination with a super acid catalyst, Lewis acid, Bronsted acids, or mixtures thereof, under conditions of reaction sufficient to form a mixture containing at least one acetal organic compound, and a gaseous product substantially free of acetylene. Preferred catalysts include boron trifluoride in methanol with mercuric oxide. Processes according to the invention are, advantageously, used for recovery of acetylene-free gaseous mixture from gaseous feedstreams containing a mixture of acetylene, a synthesis gas comprising dihydrogen and carbon monoxide, and optionally one or more members of the group consisting of dimethyl ether, formaldehyde, ethylene, and propylene.

Continuous process for recovery of acetylene-free gaseous mixture

A process of contacting a feedstream containing dioxygen, carbon monoxide, ether, and alkanol, which can be vaporized under conditions of reaction, with a blend of catalysts which are heterogeneous to the feedstream, under conditions of reaction sufficient to form a mixture containing at least one higher molecular weight oxygenated organic compound is described. In another aspect, this invention relates to a blend of catalysts consisting of at least one molecular sieve, natural or synthetic, which has been found useful for hydrocarbon conversion reactions and a catalyst comprising a metal halide or a mixed metal halide supported on active carbon, which is effective in catalyzing direct formation of organic carbonates.

A method for the highly selective production of 2,6-dimethlynaphthalene by the transmethylation of naphthalene or 2-methylnaphthalene by the use of a specific acid catalyst and a highly regeospecific methylating agent.

Selective production of 2,6-dimethylnaphthalene

A catalyzed, continuous vapor phase process to convert a C.sub.2 or higher alcohol and, optionally, one or more C.sub.1 or higher alcohols, for example methanol and ethanol, to a mixture containing at least one higher molecular weight alcohol, for example, isobutanol, over a catalyst which is essentially magnesium oxide. The process also may have a lower aldehyde and/or ketone in the feed.

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West Chicago, IL, United States of America

Gary P Hagen