Process to prepare higher ethylene amines and ethylene amine derivatives

Patent metadata

Field	Value
Publication number	US-10995077-B2
Application number	US-201716076463-A
Country	US
Kind code	B2
Filing date	Feb 10, 2017
Priority date	Feb 12, 2016
Publication date	May 4, 2021
Grant date	May 4, 2021

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 2 wherein one or more units —NH—C 2 H 4 —NH— are present as a piperazine unit or precursors thereof wherein optionally one or more units —NH—C 2 H 4 —NH— are 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 at least one of the amine-functional compound or the ethanolamine-functional compound contains a piperazine unit, and the reaction is performed in a liquid that comprises water.

First claim

The invention claimed is:

1. A process for preparing a piperazine unit-containing ethyleneamine of the formula:

wherein R 1 and R 2 are independently selected form H and —(C 2 H 4 NH) p H,
wherein p is at least 1 and optionally i) one or more units —NH—C 2 H 4 —NH— are present as a piperazine unit:

or a cyclic ethylene urea unit:

or ii) a carbonyl moiety is present between two —NH—C 2 H 4 —NH— units;
said process comprising reacting an ethanolamine-functional compound and an amine-functional compound in the presence of a carbon oxide delivering agent, in a liquid that comprises water, and at a temperature of at least 160° C. for a reaction time of between 5 minutes and 10 hours;
wherein:
the ethanolamine functional compound contains a hydroxyl group linked via an ethylene group to an amine group, or a linear or cyclic carbamate derivative thereof, or is UAEEA (the cyclic urea of aminoethylethanolamine)

the amine functional compound contains no alcohol groups, and contains one or more amine groups, or the amine functional compound is the cyclic urea of ethylenediamine (EU)

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 at least one of the amine-functional compound or the ethanolamine-functional compound contains a piperazine unit; and
wherein the molar ratio of water to the amine-functional compound is greater than 0.2:1 and less than 4.8:1.

2. 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 and one or more —NH—C 2 H 4 —NH— units are present as a piperazine unit; wherein optionally one or more —NH—C 2 H 4 —NH— units may be present as a cyclic ethylene urea unit; and wherein optionally one or more —O—C 2 H 4 —NH— units are present as a cyclic ethylene carbamate unit.

3. The process of claim 1 , wherein the amine-functional compound is selected from the group consisting of (a) piperazine (PIP), (b) aminoethylpiperazine (AEP), (c) diaminoethylpiperazine (DAEP), (d) piperazinoethyl ethylenediamine (PEEDA), and a linear urea of any one of (a)-(d).

4. The process of claim 1 , wherein the ethanolamine-functional compound is monoethanolamine (MEA) or a cyclic or linear carbamate thereof; or aminoethylethanolamine (AEEA) or a cyclic or linear carbamate or urea derivative thereof.

5. The process of claim 1 , wherein the liquid comprises at least 75 wt-% of water based on a total weight of the liquid.

6. The process of claim 1 , wherein the molar ratio of ethanolamine-functional compound to amine-functional compound is at least 0.7:1.

7. The process of claim 1 , wherein the molar ratio of carbon oxide delivering agent to amine functional compound is at least 0.2:1.

8. The process of claim 1 , wherein the molar ratio of ethanolamine-functional compound to amine-functional compound is between 0.8 and 5:1 and the molar ratio of carbon oxide delivering agent to amine functional compound is between 0.5:1 and 20:1.

9. The process of claim 1 , wherein the molar ratio of ethanolamine-functional compound to amine-functional compound is between 0.7:1 and 2:1 and the molar ratio of carbon oxide delivering agent to amine-functional compound is between 0.7:1 and 3:1.

10. 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 a carbamate adduct.

11. The process of claim 1 , wherein the ethanolamine-functional compound is monoethanolamine (MEA), the cyclic carbamate of MEA (CMEA) or a mixture thereof and the amine-functional compound is PIP or a mixture of PIP, ethylenediamine (EDA) and the cyclic urea of EDA (EU), and wherein the molar ratio of MEA+CMEA to EDA+EU+PIP is higher than 2.

12. A process for producing an ethylene amine, said process comprising:
(a) preparing an ethylene amine compound containing a cyclic ethylene urea moiety according to the process of claim 1 ; and
(b) converting said ethylene amine compound containing a cyclic ethylene urea moiety into its corresponding ethylene amine.

13. The process of claim 1 , wherein the molar ratio of water to the amine-functional compound is greater than 0.5:1.

14. The process of claim 1 , wherein the molar ratio of water to the amine-functional compound is greater than 1:1.

15. The process of claim 11 , wherein the molar ratio of MEA+CMEA to EDA+EU+PIP is higher than 3.

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
• Ehlers Ina

Classifications

• C07D233/36 Primary

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

• C07D295/13 Primary

  to an acyclic saturated chain · CPC title

• C07D295/023

  Preparation; Separation; Stabilisation; Use of additives · CPC title