Ethyl Corporation

Duane C Hargis

Michael Dubeck

Lawrence J Kehoe

Ronald L Shubkin

Monocarboxylic acids or esters thereof are reduced to aldehydes using hydrogen and a vanadium catalyst. For example, meta-phenoxybenzoic acid can be effectively converted to meta-phenoxybenzaldehyde in a vapor phase process using hydrogen as the carrier gas/reductant and a catalyst composed at least initially of vanadium pentoxide, either supported or unsupported.

Process for catalytic reduction of carboxylic acids to aldehydes

By reacting a primary aromatic amine with a dialkyl ether in the presence of a titanium dioxide alkylation catalyst having a surface area below about 130 square meters per gram, preferably in the anatase crystallographic form, at a suitably elevated temperature above about 300.degree. C., the amount of exclusively ring-alkylated product formed exceeds the amount of exclusively N-alkylated product formed.

Alkylation of aromatic amines

Compounds containing at least one N,N-dialkylatable amino or amido group (e.g., aniline, dodecylamine, acetamide) are converted in a highly efficient manner into gem cyclodialkylated compounds by reaction with an unstrained cyclic ether (e.g., tetrahydrofuran) or a polyol (e.g., 1,4-butane diol) cyclizable to an unstrained ether using titanium dioxide catalysts that have prior to use:

Gem cyclodialkylation of amines and amides

An ethanolamine, preferably diethanolamine, is converted to triethylenediamine or 1,4-bis(2-hydroxyethyl)piperazine, or both by pyrolysis using a B-subgroup metal oxide such as titanium dioxide or zirconium dioxide, as catalyst. In addition it has also been discovered that 1,4-bis(2-hydroxyethyl)piperazine and N-(2-hydroxyethyl)piperazine can be converted in high yields and conversions into triethylenediamine by pyrolysis using the same type of catalyst. When using an ethanolamine as the feedstock and a Group IV-B metal oxide as the catalyst, the process usually results in the coproduction of triethylenediamine and 1,4-bis(2-hydroxyethyl)piperazine, and the latter can be recovered and used as a raw material for the production of additional triethylenediamine, as by recycle to the same reactor or as feedstock to an additional pyrolysis reactor.

Production of triethylenediamine

Aromatic amines are alkylated by reaction with an acyclic ether or an unstrained cyclic ether in the presence of a B-subgroup metal oxide alkylation catalyst, preferably a Group IV-B metal oxide with or without a minor proportion of a Group VI-B or Group VIII metal oxide, so that alkylation of the aromatic amine occurs. Under most reaction conditions ether alkylating agents such as diethyl ether not consumed in the alkylation reaction pass through the reaction zone undecomposed and thus can be readily recovered for recycle or other use.

Catalytic alkylation of aromatic amines with ethers

Amines and amides are N,N-cyclodialkylated by reaction with an unstrained cyclic ether in the presence of a B-subgroup metal oxide alkylation catalyst, preferably a Group IV-B metal oxide such as titanium dioxide.

Aromatic amines are alkylated by reaction with an alcohol in the presence of a Group V-B metal oxide alkylation catalyst, preferably a major proportion of a Group V-B metal oxide such as V.sub.2 O.sub.5 in combination with a minor proportion of an A-subgroup metal oxide such as SnO.sub.2, so that alkylation of the aromatic amine occurs. Under most reaction conditions a considerable portion of the alcohol alkylating agent such as ethanol not consumed in the alkylation reaction passes through the reaction zone undecomposed and thus can be readily recovered for recycle or other use.

Catalytic alkylation of aromatic amines with alkanols

Alkylation of aromatic amines with ethers in the presence of iron oxide catalysts is described. By means of the process aniline, o-toluidine, and the like can be selectively orthoalkylated with such ethers as dimethyl ether, diethyl ether, tetrahydrofuran, and 1,4-dioxane at elevated temperatures in the presence of a catalyst containing iron oxide. With ethers such as dipropyl ether, diisopropyl ether and dibenzyl ether, N-alkylation is the predominant reaction. By appropriately modifying the iron oxide catalyst the process can be rendered selective for the para-alkylation of the amine. An advantage of the process is that the unreacted ether is not extensively decomposed in the process and thus can be recovered for recycle or other use.

Alkylation process

Aromatic amines are alkylated by reaction with an alcohol in the presence of a Group VII-B metal oxide alkylation catalyst, preferably a major proportion of a Group VII-B metal oxide such as MnO.sub.2 in combination with a minor proportion of a Group VIII metal oxide such as Fe.sub.2 O.sub.3, so that alkylation of the aromatic amine occurs. Under most reaction conditions a considerable portion of the alcohol alkylating agent such as ethanol not consumed in the alkylation reaction passes through the reaction zone undecomposed and thus can be readily recovered for recycle or other use.

One or more aldehydes or ketones, or both, are produced by pyrolyzing an alcohol having at least two carbon atoms or an aldehyde having at least two carbon atoms, or both, over a Group VIII metal oxide catalyst, preferably a catalyst composed predominantly of iron oxide, notably ferric oxide. Preferably, the catalyst additionally contains a minor proportion of a Group IV-A metal oxide, most preferably germanium dioxide. The process provides a good yield of lower molecular weight aldehydes, such as formaldehyde, or higher molecular weight ketones, such as acetone, 2-pentanone and the like. Selective manufacture of products enriched either in aldehyde or in ketone can be achieved by a simple adjustment in the reaction conditions employed.

Production of aldehydes and ketones

A process for the selective formation of ethanol and methyl acetate by contacting methanol, hydrogen and carbon monoxide with a catalyst comprising rhodium and iron in the reduced state deposited on a support of alumina containing a minor amount of an alkaline metal at reaction conditions correlated so as to favor the formation of a substantial proportion of ethanol and methyl acetate.

Catalytic process for the selective formation of ethanol and methyl

A process for selectively preparing ethanol by contacting methanol, hydrogen and carbon monoxide with a solid catalyst comprising rhodium and iron in the reduced state deposited on a support of alumina impregnated with a promoter amount of a heterocyclic amine at reaction conditions correlated so as to favor the formation of a substantial proportion of ethanol.

Ethanol from methanol and synthesis gas

Catalyst for converting methanol and synthesis gas to ethanol

Catalytic composition for the selective formation of ethanol and methyl

A process for selectively preparing alpha-olefins having from 2 to about 22 carbon atoms by contacting a gaseous mixture containing carbon monoxide and hydrogen with an iron titanate-alkali metal hydroxide catalyst at reaction conditions correlated so as to favor the formation of a substantial proportion of such alpha-olefin product.

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Baton Rouge, LA, United States of America

Duane C Hargis