Process to prepare higher ethylene amines and ethylene amine derivatives

Patent metadata

Field	Value
Publication number	US-10844001-B2
Application number	US-201716074485-A
Country	US
Kind code	B2
Filing date	Feb 10, 2017
Priority date	Feb 12, 2016
Publication date	Nov 24, 2020
Grant date	Nov 24, 2020

Abstract

The present invention relates to a process to prepare ethylene amines of the formula NH2—(C2H4—NH—)pH wherein p is at least 3 or derivatives thereof wherein one or more units —NH—C2H4—NH— may be present as a cyclic ethylene urea unit or between two units —NH—C2H4—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 carbon oxide delivering agent to amine-functional compound is at least 0.6 to 1.

First claim

The invention claimed is:

1. A process of preparing (i) ethylene amines of the formula: NH 2 —(C 2 H 4 —NH—) p H wherein p is at least 3, (ii) derivatives thereof wherein one or more —NH—C 2 H 4 —NH— units are present as a cyclic ethylene urea unit

and/or (iii) derivatives thereof wherein a carbonyl moiety is present between two —NH—C 2 H 4 —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—C 2 H 4 —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—C 2 H 4 —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.

2. The process of claim 1 wherein the molar ratio of carbon oxide delivering agent to amine functional compound is between 0.8:1 and 20:1.

3. The process of claim 1 wherein in at least part of the ethanol-amine functional compound one or more —O—C 2 H 4 —NH— units are present as cyclic ethylene carbamate units or, if present, one or more —N—C 2 H 4 —N— units are present in the form of cyclic ethylene urea units.

4. The process of claim 1 wherein in at least part of the amine-functional compound one or more —N—C 2 H 4 —N— units are present in the form of cyclic ethylene urea units.

5. The process of claim 1 wherein the ethanolamine-functional compound is of the formula HO—(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 —O—C 2 H 4 —NH— or —N—C 2 H 4 —N— units may be present as a cyclic ethylene urea or cyclic ethylene carbamate units.

6. 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.

7. The process of claim 6 wherein the ratio of AEEA, UAEEA+CAEEA to EDA+EU is equal to or higher than 1.

8. 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.

9. The process of claim 8 wherein the ratio of MEA+CMEA to DETA+UDETA is higher than 1.

10. 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 EDA (ethylenediamine), EU (ethyleneurea) or a mixture thereof.

11. The process of claim 10 wherein the ratio of MEA+CMEA to EDA+EU is higher than 2.

12. The process of claim 9 wherein the ratio of MEA+CMEA to DETA+UDETA is higher than 2.

13. The process of claim 11 wherein the ratio of MEA+CMEA to EDA+EU is higher than 3.

Assignees

• Nouryon Chemicals Int Bv

Inventors

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

Classifications

• C07D233/36

  with hydrocarbon radicals, substituted by nitrogen atoms, attached to ring nitrogen atoms · CPC title

• C07C211/14

  Amines containing amino groups bound to at least two aminoalkyl groups, e.g. diethylenetriamines · CPC title

• C07C273/1836

  from derivatives of carbamic acid · CPC title

• C07C275/14

  being further substituted by nitrogen atoms not being part of nitro or nitroso groups · CPC title

• C07C273/1863

  from urea · CPC title