The present invention relates to novel Ruthenium complexes of formulae A1-A4 and their use, inter alia, for (1) dehydrogenative coupling of alcohols to esters; (2) hydrogenation of esters to alcohols (including hydrogenation of cyclic esters (lactones) or cyclic di-esters (di-lactones), or polyesters); (3) preparing amides from alcohols and amines—(including the preparation of polyamides (e.g., polypeptides) by reacting dialcohols and diamines and/or polymerization of amino alcohols and/or forming cyclic dipeptides from p-aminoalcohols; (4) hydrogenation of amides (including cyclic dipeptides, polypeptides and polyamides) to alcohols and amines; (5) hydrogenation of organic carbonates (including polycarbonates) to alcohols or hydrogenation of carbamates (including polycarbamates) or urea derivatives to alcohols and amines; (6) dehydrogenation of secondary alcohols to ketones; (7) amidation of esters (i.e., synthesis of amides from esters and amines); (8) acylation of alcohols using esters; (9) coupling of alcohols with water and a base to form carboxylic acids; and (10) preparation of amino acids or their salts by coupling of amino alcohols with water and a base. The present, invention further relates to the use of certain known Ruthenium complexes for the preparation of amino acids or their salts from amino alcohols.

Disclosed is a composite catalyst, comprising carbon in a continuous phase and Raney alloy particles in a dispersed phase. The Raney alloy particles are dispersed evenly or unevenly in the carbon in a continuous phase, and the carbon in a continuous phase is obtained by carbonizing at least one carbonizable organic substance. The catalyst has good particle strength, high catalytic activity, and good selectivity.

Disclosed is a composite catalyst, comprising carbon in a continuous phase and Raney alloy particles in a dispersed phase. The Raney alloy particles are dispersed evenly or unevenly in the carbon in a continuous phase, and the carbon in a continuous phase is obtained by carbonizing at least one carbonizable organic substance. The catalyst has good particle strength, high catalytic activity, and good selectivity.

A process for preparing amides by reacting a primary amine and a primary alcohol in the presence of a Ruthenium complex to generate the amide and molecular hydrogen. Primary amines are directly acylated by equimolar amounts of alcohols to produce amides and molecular hydrogen (the only byproduct) in high yields and high turnover numbers. Also disclosed are processes for hydrogenation of amides to alcohols and amines; hydrogenation of organic carbonates to alcohols; hydrogenation of carbamates or urea derivatives to alcohols and amines; amidation of esters; acylation of alcohols using esters; coupling of alcohols with water and a base to form carboxylic acids; dehydrogenation of beta-amino alcohols to form pyrazines and cyclic dipeptides; and dehydrogenation of secondary alcohols to ketones. These reactions are catalyzed by a Ruthenium complex which is based on a dearomatized PNN-type ligand of formula A1 or precursors thereof of formulae A2 or A3.

A process for preparing amides by reacting a primary amine and a primary alcohol in the presence of a Ruthenium complex to generate the amide and molecular hydrogen. Primary amines are directly acylated by equimolar amounts of alcohols to produce amides and molecular hydrogen (the only byproduct) in high yields and high turnover numbers. Also disclosed are processes for hydrogenation of amides to alcohols and amines; hydrogenation of organic carbonates to alcohols; hydrogenation of carbamates or urea derivatives to alcohols and amines; amidation of esters; acylation of alcohols using esters; coupling of alcohols with water and a base to form carboxylic acids; dehydrogenation of beta-amino alcohols to form pyrazines and cyclic dipeptides; and dehydrogenation of secondary alcohols to ketones. These reactions are catalyzed by a Ruthenium complex which is based on a dearomatized PNN-type ligand of formula A1 or precursors thereof of formulae A2 or A3.

A process can be used to prepare alkenes by catalytic conversion of synthesis gas to a first mixture comprising alkenes and alcohols. The alcohols present in the first mixture are converted to the corresponding alkenes by dehydration in a subsequent step. At least one alkene having two to four carbon atoms is obtained as isolated product from a product mixture by processing thereof and/or separation steps. In the catalytic conversion, a catalyst is preferably used that comprises grains of non-graphitic carbon having cobalt nanoparticles dispersed therein. The cobalt nanoparticles have an average diameter d.sub.p of 1-20 nm. An average distance D between individual cobalt nanoparticles in the grains is 2-150 nm. A combined total mass fraction ω of metal in the grains is from 30%-70% by weight of a total mass of the grains such that 4.5 dp/ω>D≥0.25 dp/ω.

A process can be used to prepare alkenes by catalytic conversion of synthesis gas to a first mixture comprising alkenes and alcohols. The alcohols present in the first mixture are converted to the corresponding alkenes by dehydration in a subsequent step. At least one alkene having two to four carbon atoms is obtained as isolated product from a product mixture by processing thereof and/or separation steps. In the catalytic conversion, a catalyst is preferably used that comprises grains of non-graphitic carbon having cobalt nanoparticles dispersed therein. The cobalt nanoparticles have an average diameter d.sub.p of 1-20 nm. An average distance D between individual cobalt nanoparticles in the grains is 2-150 nm. A combined total mass fraction ω of metal in the grains is from 30%-70% by weight of a total mass of the grains such that 4.5 dp/ω>D≥0.25 dp/ω.

A method of producing a fuel additive includes producing a first product stream comprising butadiene by passing a feed stream comprising C4 hydrocarbons through a steam cracker; transforming greater than or equal to 90 weight % of the butadiene in the first product stream into a second product stream by passing the first product stream through a first hydrogenation unit, wherein the second product stream comprises 1-butene, 2-butene, n-butane, isobutylene, isobutane, or a combination thereof; and converting the second product stream into the fuel additive by passing the second product stream through a fuel additive synthesis unit with an acid catalyst.

A method of producing a fuel additive includes producing a first product stream comprising butadiene by passing a feed stream comprising C4 hydrocarbons through a steam cracker; transforming greater than or equal to 90 weight % of the butadiene in the first product stream into a second product stream by passing the first product stream through a first hydrogenation unit, wherein the second product stream comprises 1-butene, 2-butene, n-butane, isobutylene, isobutane, or a combination thereof; and converting the second product stream into the fuel additive by passing the second product stream through a fuel additive synthesis unit with an acid catalyst.

A process for simultaneously hydrating and oligomerizing a hydrocarbon feed comprising mixed olefins incudes the steps of: (a) introducing the hydrocarbon feed in the presence of water into a fixed bed; (b) contacting the hydrocarbon feed with a catalyst within said fixed bed reactor, where the catalyst is of the type that hydrates the mixed olefins to form mixed alcohols and oligomerizes at least a portion of the mixed olefins into oligomers to produce a first product stream that includes an organic phase and an aqueous phase; (c) introducing the first product stream into a first separator which separates the organic phase from the aqueous phase; (d) introducing the separated organic phase into a second separator which separates unreacted olefins from mixed alcohols and one or more oligomers which comprise a final product stream; and (e) introducing the separated aqueous phase into a third separator which separates an alcohol-water azeotrope component from water.