Process to prepare higher ethylene amines and ethylene amine derivatives

A process of preparing (i) ethylene amines of the formula:

• NH2—(C2H4—NH—)pH wherein p is at least 3, (ii) derivatives thereof wherein one or more —NH—C2H4—NH— units are present as a cyclic ethylene urea unit
• and/or (iii) derivatives thereof wherein a carbonyl moiety is present between two —NH—C2H4—NH— units,
• said process comprising the following steps:
• (a) reacting an ethanolamine-functional compound and an amine-functional compound in the presence of a carbon oxide delivering agent to obtain a mixture of products, at least some of which products are said derivatives thereof wherein one or more units —NH—C2H4—NH— are present as a cyclic ethylene urea unit, wherein for said reacting the molar ratio of carbon oxide delivering agent to amine-functional compound is at least 0.8:1;
• and
• (b) converting at least some of said derivatives thereof wherein one or more units —NH—C2H4—NH— are present as a cyclic ethylene urea unit to the corresponding ethylene amines;
• wherein:
• the ethanolamine functional compound contains a hydroxyl group linked via an ethylene group to an amine group, or its carbamate equivalent, or the ethanolamine functional compound is UAEEA (the urea of aminoethylethanolamine);
• the amine functional compound contains no alcohol groups, and contains at least two primary amine groups and optionally more primary, secondary and/or tertiary amine groups, wherein the amine groups are linked to one another via ethylene groups, and optionally by a carbonyl moiety;
• and
• the carbon oxide delivering agent is carbon dioxide or an organic compound selected from urea, linear and cyclic alkylene ureas, mono- or di-substituted alkylene ureas, alkyl and dialkyl ureas, linear and cyclic carbamates and organic carbonates, and derivatives or precursors thereof selected from carbonate salts, bicarbonate salts and carbamic acids and their salts.