Process and catalyst for synthesizing aliphatic, cyclic and aromatic alkanolamines and alkyleneamines

Abstract

The invention provides a process for synthesizing alkanolamines and/or alkyleneamines by reacting either an alkane, an alkene, or both with a source of oxygen and a source of nitrogen and, optionally, additional hydrogen to convert the alkane and/or alkene by selective partial oxidative amination to at least one of the desired end products. The invention further provides a regenerable catalyst for use in synthesizing alkanolamines and/or alkyleneamines by selective partial oxidative amination of alkanes and/or alkenes.

1 . A process for synthesizing at least one of an alkanolamine and an alkyleneamine, said process including the step of: 
 reacting an alkane and/or an alkene with a source of oxygen, a source of nitrogen and, optionally, additional hydrogen to convert said alkane and/or alkene by partial oxidative amination to at least one of said alkanolamine and alkyleneamine.    
     
     
         2 . The process of    claim 1   , wherein the source of nitrogen is at least one of ammonia, hydrazine, amines, and nitrous oxide in the presence of a reducing gas.  
     
     
         3 . The process of    claim 1   , wherein the source of oxygen is at least one of oxygen, ozone, oxides of nitrogen, water, and alcohols.  
     
     
         4 . The process of    claim 1   , wherein the oxygen is provided by at least one metal oxide catalyst.  
     
     
         5 . The process of    claim 4   , wherein the metal oxide catalyst comprises at least one metal oxide that is reduced by reaction with a hydrocarbon moiety to a lower oxidation state such that the metal oxide provides a lower standard free energy for the partial oxidative amination of the alkane and/or alkene.  
     
     
         6 . The process of    claim 4   , wherein the catalyst is regenerable.  
     
     
         7 . The process of    claim 4   , wherein the alkane and/or alkene is reacted with the source of nitrogen over the catalyst in a circulating fluidized bed reactor.  
     
     
         8 . The process of    claim 6   , wherein the metal oxide catalyst is regenerated by exposing the catalyst to a source of oxygen.  
     
     
         9 . The process of    claim 1   , wherein ethane and/or ethylene is reacted with ammonia and oxygen to form at least one of monoethanolamine and ethylenediamine.  
     
     
         10 . The process of    claim 2   , wherein the ammonia is provided at a partial pressure which determines the ratio of alkanolamine and alkyleneamine synthesized.  
     
     
         11 . The process of    claim 1   , wherein in addition to a source of nitrogen and a source of oxygen the alkane and/or alkene is reacted with a source of hydrogen.  
     
     
         12 . The process of    claim 11   , wherein a hydrogenation/dehydrogenation catalyst is present with the source of hydrogen.  
     
     
         13 . The process of    claim 1   , wherein the reaction is carried out in one of gas, liquid, multi-phase, and super critical media.  
     
     
         14 . The process of    claim 9   , wherein the alkanolamine is monoethanolamine which is reacted further to form at least one of diethanolamine and triethanolamine.  
     
     
         15 . A regenerable catalyst for use in synthesizing at least one of an alkanolamine and/or alkyleneamine by partial oxidative amination of alkanes and/or alkenes, said catalyst comprising at least one of: 
 a reducible metal oxide that is reduced by reaction with a hydrocarbon moiety to a lower oxidative state, such that the metal oxide provides a lower standard free energy for the partial oxidative amination of alkanes and alkenes: and    a hydrogenation/dehydrogenation metal capable of generating at least one of a hydroperoxo and peroxo intermediate.    
     
     
         16 . The catalyst of    claim 15   , wherein the reducible metal oxide is selected from the group consisting of oxides of cerium, iron, copper, nickel, lead, cadmium, molybdenum, vanadium, bismuth, manganese, barium, cobalt, strontium, tungsten, samarium, osmium, rhenium, rare earth elements, and mixtures of these oxides.  
     
     
         17 . The catalyst of    claim 16   , wherein the metal oxided is selected from the group consisting of: NiO, PbO, CdO, MoO 3 , V 2 O 4 , V 2 O 5 , BiO, Bi 2 O 3 , CuO, Cu 2 0, MnO 2 , Mn 2 O 3 , Mn 3 O 4  BaO2, Co 3 O 4 SrO 2 , WO 2 , WO 3 , SnO2, CeO 2 , OsO 4 , Re 2 O 7 , Fe 2 O 3 , Fe 3 O 4 , rare earth oxides, and mixtures thereof.  
     
     
         18 . The catalyst of    claim 15   , wherein the hydrogenation/dehydrogenation metal is selected from the group consisting of: nickel, palladium, platinum, cobalt, rhodium, iridium, iron, ruthenium, copper, zinc, gold, and silver and mixtures thereof.  
     
     
         19 . The catalyst of    claim 15    further comprising a carrier for supporting at least one of the reducible metal oxide and the hydrogenation/dehydrogenation metal.  
     
     
         20 . The catalyst of    claim 19   , wherein the carrier is selected from the group consisting of: cerias, titanias, zirconias, silicas, aluminas, ∝-alumina, silicon carbide, aluminum phosphate molecular sieves (AlPO's), high silica molecular sieve zeolites, MCM-type large pore zeolites, mixtures thereof.