Process to prepare ethylene amines and ethylene amine derivatives

Patent metadata

Field	Value
Publication number	US-11267792-B2
Application number	US-201816630291-A
Country	US
Kind code	B2
Filing date	Jul 3, 2018
Priority date	Jul 10, 2017
Publication date	Mar 8, 2022
Grant date	Mar 8, 2022

Abstract

A process is provided for preparing ethyleneamines 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 piperazine unit or between two units —NH—C2H4—NH— a carbonyl moiety is present. The process includes reacting an ethanolamine-functional compound OH—(C2H4—NH—)qH wherein q is at least 2, an amine-functional compound NH2—(C2H4—NH—)rH wherein r is at least 1, in the presence of a carbon oxide delivering agent, wherein the molar ratio of ethanolamine-functional compound to amine-functional compound is from about 0.05:1 to about 0.7:1 and the molar ratio of carbon oxide delivering agent to amine-functional compound is higher than the molar ratio of ethanolamine-functional compound to amine-functional compound, provided that the process does not comprise reacting 3 moles of ethylenediamine (EDA) and 1 mole of AEEA (aminoethylethanolamine) in the presence of 1.65 moles of urea at 280 deg C. for 2 hours.

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, or derivatives thereof wherein one or more units —NH—C 2 H 4 —NH— may be present as a cyclic ethylene urea unit

or piperazine unit

or between two units —NH—C 2 H 4 —NH— a carbonyl moiety is present, the process comprising:
reacting an ethanolamine-functional compound HO—(C 2 H 4 —NH—) q H wherein q is at least 2, an amine-functional compound NH 2 —(C 2 H 4 —NH—) r H wherein r is at least 1, in the presence of a carbon oxide delivering agent, wherein the molar ratio of ethanolamine-functional compound to amine-functional compound is from 0.05:1 to 0.7:1 and the molar ratio of carbon oxide delivering agent to amine-functional compound is higher than the molar ratio of ethanolamine-functional compound to amine-functional compound, provided that the process does not comprise reacting 3 moles of ethylenediamine (EDA) and 1 mole of AEEA (aminoethylethanolamine) in the presence of 1.65 moles of urea at 280 deg C. for 2 hours.

2. The process of claim 1 wherein the molar ratio of carbon oxide delivering agent to amine-functional compound is at least 10% higher than the molar ratio of ethanolamine-functional compound to amine-functional compound.

3. The process of claim 1 wherein the molar ratio of carbon oxide delivering agent to amine-functional compound is at least 50% higher than the molar ratio of ethanolamine-functional compound to amine-functional compound.

4. The process of claim 1 wherein the molar ratio of carbon oxide delivering agent to amine-functional compound is up to 500% higher than the molar ratio of ethanolamine-functional compound to amine-functional compound.

5. 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 piperazine unit

or between two units NH—C 2 H 4 —NH— a carbonyl moiety is present, the process comprising:
reacting an ethanolamine-functional compound HO—(C2H 4 —NH—) q H wherein q is at least 2, an amine-functional compound NH 2 —(C 2 H 4 —NH—) r H wherein r is at least 1, in the presence of a carbon oxide delivering agent, wherein the molar ratio of ethanolamine-functional compound to amine-functional compound is from 0.1 to 0.5 and the molar ratio of carbon oxide delivering agent to amine-functional compound is higher than the molar ratio of ethanolamine-functional compound to amine-functional compound, provided that the process does not comprise reacting 3 moles of ethylenediamine (EDA) and 1 mole of AEEA (aminoethylethanolamine) in the presence of 1.65 moles of urea at 280 deg C. for 2 hours.

6. The process of claim 1 further comprising providing a carbamate adduct to the reaction of the ethanolamine-functional compound, the amine-functional compound, and the carbon oxide delivering agent.

7. The process of claim 1 further comprising providing an urea adduct to the reaction of the ethanolamine-functional compound, the amine-functional compound, and the carbon oxide delivering agent.

8. The process of claim 1 further comprising converting the obtained cyclic ethylene urea into its corresponding ethylene amine.

9. 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.

10. 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 DETA (diethylenetriamine), UDETA, (the urea of DETA) or a mixture thereof.

11. The process of claim 5 wherein the molar ratio of carbon oxide delivering agent to amine-functional compound is at least 10% higher than the molar ratio of ethanolamine-functional compound to amine-functional compound.

12. The process of claim 5 wherein the molar ratio of carbon oxide delivering agent to amine-functional compound is at least 50% higher than the molar ratio of ethanolamine-functional compound to amine-functional compound.

13. The process of claim 5 wherein the molar ratio of carbon oxide delivering agent to amine-functional compound is up to 500% higher than the molar ratio of ethanolamine-functional compound to amine-functional compound.

14. The process of claim 5 further comprising providing a carbamate adduct to the reaction of the ethanolamine-functional compound, the amine-functional compound, and the carbon oxide delivering agent.

15. The process of claim 5 further comprising providing a urea adduct to the reaction of the ethanolamine-functional compound, the amine-functional compound, and the carbon oxide delivering agent.

16. The process of claim 5 further comprising converting the obtained cyclic ethylene urea into its corresponding ethylene amine.

17. The process of claim 5 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.

18. The process of claim 5 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 DETA (diethylenetriamine), UDETA, (the urea of DETA) or a mixture thereof.

Assignees

• Nouryon Chemicals Int Bv

Inventors

• Raaijmakers Michiel Jozef Thomas
• Ten Kate Antoon Jacob Berend
• Veneman Rens
• Lake Karl Fredrik
• Jovic Slavisa
• Kantzer Eike Nicolas
• Ehlers Ina
• Edvinsson Rolf Krister
• Skansen Björn Patrik
• Sarning Michael Bertil Einar
• Adrian Meredith Jenny Valborg Therese
• Van Dam Hendrik

Classifications

• C07D233/34

  Ethylene-urea · CPC title

• Y02P20/582

  Recycling of unreacted starting or intermediate materials · CPC title

• C07C209/16

  with formation of amino groups bound to acyclic carbon atoms or to carbon atoms of rings other than six-membered aromatic rings · CPC title

• C07C213/08

  by reactions not involving the formation of amino groups, hydroxy groups or etherified or esterified hydroxy groups · CPC title

• C07D241/04 Primary

  having no double bonds between ring members or between ring members and non-ring members · CPC title