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.

The present invention provides a system and method of storing hydrogen (H.sub.2) and releasing it on demand, comprising and making use of diaminoalkanes and alcohols, or aminoalcohols as liquid-organic hydrogen carrier systems (LOHC). 2-amino-ethanol (AE) or its N-methyl derivative 2-(methylamino)ethanol undergo catalytic dehydrogenation to form a cyclic dipeptide (glycine anhydride—GA) or its N,N-dimethyl derivative (N,N-dimethyl GA) with release of hydrogen. Similarly, ethylenediamine (ED) and ethanol undergo catalytic dehydrogenation to form N,N′-diacetylethylenediamine (DAE) with release of hydrogen. Glycine anhydride (GA) or N,N-dimethyl-GA may be hydrogenated back to 2-aminoethanol (AE) or 2-(methylamino)ethanol, respectively, each of which functions as a hydrogen storage system. N,N′-diacetylethylenediamine (DAE) may be hydrogenated back to ED and ethanol, which functions as a hydrogen storage system. These reactions may be catalyzed by a variety of compounds or complexes, including Ruthenium complexes as described herein.

The present invention provides a system and method of storing hydrogen (H.sub.2) and releasing it on demand, comprising and making use of diaminoalkanes and alcohols, or aminoalcohols as liquid-organic hydrogen carrier systems (LOHC). 2-amino-ethanol (AE) or its N-methyl derivative 2-(methylamino)ethanol undergo catalytic dehydrogenation to form a cyclic dipeptide (glycine anhydride—GA) or its N,N-dimethyl derivative (N,N-dimethyl GA) with release of hydrogen. Similarly, ethylenediamine (ED) and ethanol undergo catalytic dehydrogenation to form N,N′-diacetylethylenediamine (DAE) with release of hydrogen. Glycine anhydride (GA) or N,N-dimethyl-GA may be hydrogenated back to 2-aminoethanol (AE) or 2-(methylamino)ethanol, respectively, each of which functions as a hydrogen storage system. N,N′-diacetylethylenediamine (DAE) may be hydrogenated back to ED and ethanol, which functions as a hydrogen storage system. These reactions may be catalyzed by a variety of compounds or complexes, including Ruthenium complexes as described herein.

Production of 1,3-butadiene ethanol, that is more than 50% of the total weight of feedstock: A) conversion of feedstock and of ethanol effluent from separation B to a conversion effluent being a majority of 1,3-butadiene, water and ethylene, and to a hydrogen effluent, operating at a pressure between 0.1 and 1.0 MPa, a temperature between 300 and 500° C. in the presence of at least one catalyst; B) separation of conversion effluent originating from A and hydration effluent from C to an ethanol effluent, a butadiene effluent, a water effluent and an ethylene effluent; C) hydration of ethylene fed by ethylene effluent and/or water effluent both from separation B, to produce an ethanol hydration effluent then being recycled to separation B.

Production of 1,3-butadiene ethanol, that is more than 50% of the total weight of feedstock: A) conversion of feedstock and of ethanol effluent from separation B to a conversion effluent being a majority of 1,3-butadiene, water and ethylene, and to a hydrogen effluent, operating at a pressure between 0.1 and 1.0 MPa, a temperature between 300 and 500° C. in the presence of at least one catalyst; B) separation of conversion effluent originating from A and hydration effluent from C to an ethanol effluent, a butadiene effluent, a water effluent and an ethylene effluent; C) hydration of ethylene fed by ethylene effluent and/or water effluent both from separation B, to produce an ethanol hydration effluent then being recycled to separation B.

The present disclosure provides high-grade ethanol production systems and methods that increase energy efficiency as compared to typical systems and methods by minimizing undesired acetal formation. The provided ethanol production method may include a low boilers removal distillation column and/or a stripper column constructed to simultaneously remove at least a portion of the acetaldehyde and at least a portion of the acetal from a feed stream in the presence of water. In some aspects, a low boilers removal process may be followed by a water removal process, which may be followed by a high boilers removal process. Acidity (e.g., carbon dioxide) may also be removed from a feed stream prior to or during the low boilers removal process. By minimizing acetal production, the provided method minimizes the amount of energy that is required to remove acetal when producing high-grade ethanol.

The present disclosure provides high-grade ethanol production systems and methods that increase energy efficiency as compared to typical systems and methods by minimizing undesired acetal formation. The provided ethanol production method may include a low boilers removal distillation column and/or a stripper column constructed to simultaneously remove at least a portion of the acetaldehyde and at least a portion of the acetal from a feed stream in the presence of water. In some aspects, a low boilers removal process may be followed by a water removal process, which may be followed by a high boilers removal process. Acidity (e.g., carbon dioxide) may also be removed from a feed stream prior to or during the low boilers removal process. By minimizing acetal production, the provided method minimizes the amount of energy that is required to remove acetal when producing high-grade ethanol.

There is provided a process for the reduction of one or more amide moieties in a compound comprising contacting the compound with hydrogen gas and a transition metal catalyst in the presence or absence of a base under conditions for the reduction an amide bond. The presently described processes can be performed at low catalyst loading using relatively mild temperature and pressures, and optionally, in the presence or absence of a base or high catalyst loadings using low temperatures and pressures and high loadings of base to effect dynamic kinetic resolution of achiral amides.

There is provided a process for the reduction of one or more amide moieties in a compound comprising contacting the compound with hydrogen gas and a transition metal catalyst in the presence or absence of a base under conditions for the reduction an amide bond. The presently described processes can be performed at low catalyst loading using relatively mild temperature and pressures, and optionally, in the presence or absence of a base or high catalyst loadings using low temperatures and pressures and high loadings of base to effect dynamic kinetic resolution of achiral amides.

A method for forming a blend of ethers from a blend of alcohols includes a step of reacting a hydrocarbon-containing gas with an oxygen-containing gas to form first product blend. The first product blend includes a blend of partially oxygenated compounds. The blend of partially oxygenated compounds is provided to a reactive distillation station where it is converted a second product blend. The second product blend typically includes a mixture of ethers. An apparatus implementing the method is also provided.