Processes for preparing amines and catalysts for use therein

Abstract

Processes for preparing an amine are described which comprise reacting a primary or secondary alcohol, aldehyde and/or ketone with hydrogen and a nitrogen compound selected from the group of ammonia, primary and secondary amines, in the presence of a zirconium dioxide-, copper- and nickel-containing catalyst. The catalytically active composition of the catalyst, before its reduction with hydrogen, comprises oxygen compounds of zirconium, of copper, of nickel, in the range from 1.0 to 5.0% by weight of oxygen compounds of cobalt, calculated as CoO, and in the range from 0.2 to 5.0% by weight of oxygen compounds of sulfur, of phosphorus, of gallium, of lead and/or of antimony, calculated in each case as H2SO4, H3PO4, Ga203, PbO and Sb203 respectively.

1 - 32 . (canceled) 
     
     
         33 . A process for preparing an amine by reacting a primary or secondary alcohol, aldehyde and/or ketone with hydrogen and a nitrogen compound selected from the group of ammonia, primary and secondary amines, in the presence of a zirconium dioxide-, copper- and nickel-containing catalyst, wherein the catalytically active composition of the catalyst, before its reduction with hydrogen, comprises oxygen compounds of zirconium, of copper, of nickel, in the range from 1.0 to 5.0% by weight of oxygen compounds of cobalt, calculated as CoO, and in the range from 0.2 to 5.0% by weight of oxygen compounds of sulfur, of phosphorus, of gallium, of lead and/or of antimony, calculated in each case as H 2 SO 4 , H 3 PO 4 , Ga 2 O 3 , PbO and Sb 2 O 3  respectively. 
     
     
         34 . The process according to  claim 33 , wherein the catalytically active composition of the catalyst, before its reduction with hydrogen, comprises in the range from 0.3 to 4.0% by weight of oxygen compounds of sulfur, of phosphorus, of gallium, of lead and/or of antimony, calculated in each case as H 2 SO 4 , H 3 PO 4 , Ga 2 O 3 , PbO and Sb 2 O 3  respectively. 
     
     
         35 . The process according to  claim 33 , wherein the catalytically active composition of the catalyst, before its reduction with hydrogen, comprises in the range from 0.5 to 3.0% by weight of oxygen compounds of sulfur, of phosphorus, of gallium, of lead and/or of antimony, calculated in each case as H 2 SO 4 , H 3 PO 4 , Ga 2 O 3 , PbO and Sb 2 O 3  respectively. 
     
     
         36 . The process according to  claim 33 , wherein the catalytically active composition of the catalyst, before its reduction with hydrogen, comprises in the range from 1.5 to 4.5% by weight of oxygen compounds of cobalt, calculated as CoO. 
     
     
         37 . The process according to  claim 33 , wherein the catalytically active composition of the catalyst, before its reduction with hydrogen, comprises in the range from 2.0 to 4.0% by weight of oxygen compounds of cobalt, calculated as CoO. 
     
     
         38 . The process according to  claim 33 , wherein the catalytically active composition of the catalyst, before its reduction with hydrogen, comprises in the range from:
 46 to 65% by weight of oxygen compounds of zirconium, calculated as ZrO 2 ,   5.5 to 18% by weight of oxygen compounds of copper, calculated as CuO, and   20 to 45% by weight of oxygen compounds of nickel, calculated as NiO.   
     
     
         39 . The process according to  claim 33 , wherein the catalytically active composition of the catalyst, before its reduction with hydrogen, comprises in the range from
 47 to 60% by weight of oxygen compounds of zirconium, calculated as ZrO 2 ,   6 to 16% by weight of oxygen compounds of copper, calculated as CuO, and   25 to 40% by weight of oxygen compounds of nickel, calculated as NiO.   
     
     
         40 . The process according to  claim 33 , wherein the catalytically active composition of the catalyst, before its reduction with hydrogen, comprises in the range from
 48 to 58% by weight of oxygen compounds of zirconium, calculated as ZrO 2 ,   7 to 14% by weight of oxygen compounds of copper, calculated as CuO, and   30 to 39% by weight of oxygen compounds of nickel, calculated as NiO.   
     
     
         41 . The process according to  claim 33 , wherein the molar ratio of nickel to copper in the catalyst is greater than 1. 
     
     
         42 . The process according to  claim 33 , wherein the catalytically active composition of the catalyst does not comprise any rhenium and/or ruthenium. 
     
     
         43 . The process according to  claim 33 , wherein the catalytically active composition of the catalyst does not comprise any iron and/or any zinc. 
     
     
         44 . The process according to  claim 33 , wherein the catalytically active composition of the catalyst does not comprise any further catalytically active component, either in elemental or in ionic form. 
     
     
         45 . The process according to  claim 33 , wherein the reaction is performed at a temperature in the range from 80 to 350° C. 
     
     
         46 . The process according to  claim 33 , wherein the reaction is performed in the liquid phase at an absolute pressure in the range from 5 to 30 MPa or in the gas phase at an absolute pressure in the range from 0.1 to 40 MPa. 
     
     
         47 . The process according to  claim 33 , wherein the nitrogen compound is used in from 0.90 to 100 times the molar amount based on the alcohol, aldehyde and/or ketone used. 
     
     
         48 . The process according to  claim 33 , wherein the nitrogen compound is used in from 1.0 to 10 times the molar amount based on the alcohol, aldehyde and/or ketone used. 
     
     
         49 . The process according to  claim 33 , wherein the catalyst is arranged in the reactor as a fixed bed. 
     
     
         50 . The process according to  claim 33 , which is performed continuously. 
     
     
         51 . The process according to  claim 50 , wherein the reaction is effected in a tubular reactor. 
     
     
         52 . The process according to  claim 50 , wherein the reaction is effected in a cycle gas method. 
     
     
         53 . The process according to  claim 33 , wherein the alcohol, aldehyde and/or the ketone is used as an aqueous solution. 
     
     
         54 . The process according to  claim 33 , wherein the ammonia, the primary or secondary amine is used as an aqueous solution. 
     
     
         55 . The process according to  claim 33  for preparing monoaminodiglycol (ADG) and morpholine by reacting diethylene glycol (DEG) with ammonia. 
     
     
         56 . The process according to  claim 33  for preparing N—(C1-4-alkyl) morpholine by reacting diethylene glycol (DEG) with mono(C1-4-alkyl)amine. 
     
     
         57 . The process according to  claim 33  for preparing 2-(2-di(C1-4-alkyl)aminoethoxy)ethanol and/or bis(2-di(C1-4-alkyl)aminoethyl)ether by reacting diethylene glycol (DEG) with di(C1-4-alkyl)amine. 
     
     
         58 . The process according to  claim 33  for preparing monoethanolamine (MEOA) and/or 1,2-ethylenediamine (EDA) by reacting monoethylene glycol (MEG) with ammonia. 
     
     
         59 . The process according to  claim 33  for preparing 1,2-ethylenediamine (EDA) by reacting monoethanolamine (MEOA) with ammonia. 
     
     
         60 . The process according to  claim 33  for preparing a polyetheramine by reacting a corresponding polyether alcohol with ammonia. 
     
     
         61 . The process according to  claim 33  for preparing piperazine and/or diethylenetriamine (DETA) by reacting N-(2-aminoethyl)ethanolamine (AEEA) with ammonia. 
     
     
         62 . The process according to  claim 33  for preparing polyisobutenamine (PIBA) by reacting polyisobutenaldehyde with ammonia. 
     
     
         63 . A catalyst, wherein the catalytically active composition of the catalyst, before its reduction with hydrogen, comprises oxygen compounds of zirconium, of copper, of nickel, in the range from 1.0 to 5.0% by weight of oxygen compounds of cobalt, calculated as CoO, and in the range from 0.2 to 5.0% by weight of oxygen compounds of sulfur, of phosphorus, of gallium, of lead and/or of antimony, calculated in each case as H 2 SO 4 , H 3 PO 4 , Ga 2 O 3 , PbO and Sb 2 O 3  respectively. 
     
     
         64 . The catalyst of  claim 63 , wherein the catalytically active composition of the catalyst, before its reduction with hydrogen, comprises in the range from 0.3 to 4.0% by weight of oxygen compounds of sulfur, of phosphorus, of gallium, of lead and/or of antimony, calculated in each case as H 2 SO 4 , H 3 PO 4 , Ga 2 O 3 , PbO and Sb 2 O 3  respectively. 
     
     
         65 . The catalyst of  claim 63 , wherein the catalytically active composition of the catalyst, before its reduction with hydrogen, comprises in the range from 0.5 to 3.0% by weight of oxygen compounds of sulfur, of phosphorus, of gallium, of lead and/or of antimony, calculated in each case as H 2 SO 4 , H 3 PO 4 , Ga 2 O 3 , PbO and Sb 2 O 3  respectively. 
     
     
         66 . The catalyst of  claim 63 , wherein the catalytically active composition of the catalyst, before its reduction with hydrogen, comprises in the range from 1.5 to 4.5% by weight of oxygen compounds of cobalt, calculated as CoO. 
     
     
         67 . The catalyst of  claim 63 , wherein the catalytically active composition of the catalyst, before its reduction with hydrogen, comprises in the range from 2.0 to 4.0% by weight of oxygen compounds of cobalt, calculated as CoO. 
     
     
         68 . The catalyst of  claim 63 , wherein the catalytically active composition of the catalyst, before its reduction with hydrogen, comprises in the range from
 46 to 65% by weight of oxygen compounds of zirconium, calculated as ZrO 2 ,   5.5 to 18% by weight of oxygen compounds of copper, calculated as CuO, and   20 to 45% by weight of oxygen compounds of nickel, calculated as NiO.   
     
     
         69 . The catalyst of  claim 63 , wherein the catalytically active composition of the catalyst, before its reduction with hydrogen, comprises in the range from
 47 to 60% by weight of oxygen compounds of zirconium, calculated as ZrO 2 ,   6 to 16% by weight of oxygen compounds of copper, calculated as CuO, and   25 to 40% by weight of oxygen compounds of nickel, calculated as NiO.   
     
     
         70 . The catalyst of  claim 63 , wherein the catalytically active composition of the catalyst, before its reduction with hydrogen, comprises in the range from
 48 to 58% by weight of oxygen compounds of zirconium, calculated as ZrO 2 ,   7 to 14% by weight of oxygen compounds of copper, calculated as CuO, and   30 to 39% by weight of oxygen compounds of nickel, calculated as NiO.   
     
     
         71 . The catalyst of  claim 63 , wherein the molar ratio of nickel to copper in the catalyst is greater than 1. 
     
     
         72 . The catalyst of  claim 63 , wherein the catalytically active composition of the catalyst does not comprise any rhenium and/or ruthenium. 
     
     
         73 . The catalyst of  claim 63 , wherein the catalytically active composition of the catalyst does not comprise any iron and/or any zinc. 
     
     
         74 . The catalyst of  claim 63 , wherein the catalytically active composition of the catalyst does not comprise any further catalytically active component, either in elemental or in ionic form.