Process to prepare higher ethylene amines and ethylene amine derivatives

Patent metadata

Field	Value
Publication number	US-10428011-B2
Application number	US-201716074496-A
Country	US
Kind code	B2
Filing date	Feb 10, 2017
Priority date	Feb 12, 2016
Publication date	Oct 1, 2019
Grant date	Oct 1, 2019

Abstract

The present invention relates to a process to prepare ethyleneamines of the formula NH 2 —(C 2 H 4 —NH—) p H wherein p is at least 3 or derivatives thereof wherein one or more units —NH—C 2 H 4 —NH— may be present as a cyclic ethylene urea unit or between two units —NH—C 2 H 4 —NH— a carbonyl moiety is present, by reacting an ethanolamine-functional compound, an amine-functional compound in the presence of a carbon oxide delivering agent, wherein the molar ratio of ethanolamine-functional compound to amine-functional compound is at least 0.7:1 and the molar ratio of carbon oxide delivering agent to amine-functional compound is at least 0.05:1.

First claim

The invention claimed is:

1. A process to prepare
ethyleneamines of the formula NH 2 —(C 2 H 4 —NH—) p H wherein p is at least 3,
derivatives of said ethyleneamines wherein one or more —NH—C 2 H 4 —NH— units are present as a cyclic ethylene urea unit

 or
derivatives of said ethyleneamines wherein a carbonyl moiety is present between two —NH—C 2 H 4 —NH— units,

said process comprising the step of reacting an ethanolamine-functional compound with an amine-functional compound in the presence of a carbon oxide delivering agent, in which
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;
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, organic carbonates, and derivatives or precursors thereof selected from carbonate salts, bicarbonate salts and carbamic acids and their salts;

wherein the molar ratio of ethanolamine-functional compound to amine-functional compound is at least 0.7:1 and the molar ratio of carbon oxide delivering agent to amine-functional compound is between 0.8:1 and 20:1.

2. The process of claim 1 wherein the molar ratio of ethanolamine-functional compound to amine-functional compound is between 0.8 and 5:1.

3. The process of claim 1 wherein the molar ratio of ethanolamine-functional compound to amine-functional compound is between 1:1 and 2:1 and the molar ratio of carbon oxide delivering agent to amine-functional compound is between 0.8:1 and 3:1.

4. The process of claim 1 wherein the ethanolamine-functional compound and the carbon oxide delivering agent are at least partly added as one compound by using either said carbamate equivalent of the ethanolamine functional compound or UAEEA.

5. The process of claim 1 wherein the ethanolamine-functional compound is of the formula OH—(C 2 H 4 —NH—) q H wherein q is at least 1 and the amine-functional compound is of the formula NH 2 —(C 2 H 4 —NH—) r H wherein r is at least 1, wherein the sum of q+r is at least 3 and wherein optionally one or more units —NH—C 2 H 4 —NH— may be present as a cyclic ethylene urea unit, or one —NH—C 2 H 4 —OH unit is present as a cyclic carbamate unit.

6. The process of claim 1 , further comprising a step of converting derivatives of ethyleneamines of the formula NH 2 —(C 2 H 4 —NH—) p H wherein p is at least 3 wherein one or more —NH—C 2 H 4 —NH— units are present as a cyclic ethylene urea unit into ethyleneamines of the formula NH 2 —(C 2 H 4 —NH—) p H.

7. The process of claim 1 wherein the ethanolamine-functional compound is AEEA (aminoethylethanolamine), CAEEA (the carbamate of aminoethylethanolamine), UAEEA (the urea of aminoethylethanolamine) or a mixture thereof, and the amine-functional compound is EDA (ethylenediamine), EU, (ethyleneurea) or a mixture thereof.

8. The process of claim 7 wherein the molar ratio of the total of AEEA, UAEEA and CAEEA to the total of EDA and EU is equal to or higher than 1:1.

9. The process of claim 1 wherein the ethanolamine-functional compound is MEA (monoethanolamine), CMEA (the carbamate of monoethanolamine) or a mixture thereof and the amine-functional compound is DETA (diethylenetriamine), UDETA (the urea of diethylenetriamine) or a mixture thereof.

10. The process of claim 9 wherein the molar ratio of the total of MEA and CMEA to the total of DETA and UDETA is higher than 1:1.

11. The process of claim 1 wherein the ethanolamine-functional compound is MEA, CMEA or a mixture thereof and the amine-functional compound EDA, EU or a mixture thereof.

12. The process of claim 11 wherein the molar ratio of the total of MEA and CMEA to the total of EDA and EU, is higher than 2:1.

13. The process of claim 10 wherein the molar ratio of the total of MEA and CMEA to the total of DETA and UDETA is higher than 2:1.

14. The process of claim 12 wherein the molar ratio of the total of MEA and CMEA to the total of EDA and EU is higher than 3:1.

15. The process of claim 1 wherein the amine-functional compound is at least partly added as a urea derivative.

Assignees

• Akzo Nobel Chemicals Int Bv
• Nouryon Chemicals Int Bv

Inventors

• Edvinsson Rolf Krister
• Kantzer Eike Nicolas
• Larsson Per Fredrik Olmo
• Lake Karl Fredrik
• Ten Kate Antoon Jacob Berend

Classifications

• B01D53/62

  Carbon oxides · CPC title

• C07C273/1854

  by reactions not involving the formation of the N-C(O)-N- moiety · CPC title

• C07C273/1863

  from urea · CPC title

• C07C273/1809

  with formation of the N-C(O)-N moiety · CPC title

• C07C209/62 Primary

  by cleaving carbon-to-nitrogen, sulfur-to-nitrogen, or phosphorus-to-nitrogen bonds, e.g. hydrolysis of amides, N-dealkylation of amines or quaternary ammonium compounds (C07C209/24 takes precedence) · CPC title