Process for manufacturing ethylene amines

Patent metadata

Field	Value
Publication number	US-10975017-B2
Application number	US-201716468514-A
Country	US
Kind code	B2
Filing date	Dec 12, 2017
Priority date	Dec 15, 2016
Publication date	Apr 13, 2021
Grant date	Apr 13, 2021

Abstract

A process for preparing polyethyleneamines of formula NH2-(CH2-CH2-NH-)pH wherein p is at least 3 and wherein one or more —NH-CH2-CH2-NH— units may be piperazine units and/or ethylene urea derivatives of these compounds, includes reacting monoethylene glycol with an amine-functional compound having at least two —NH— units, of which at least one is selected from primary amine groups and cyclic secondary amine groups, in the presence of a carbon oxide-delivering agent. The amine-functional compound includes at least one —NH-CH2-CH2-NH— unit, and one or more —NH-CH2-CH2-NH— units may be in the form of cyclic ethylene urea moieties, piperazine moieties, or linear ethylene urea moieties. The molar ratio of amine-functional compound to monoethylene glycol is above 1.2:1 and the molar ratio of carbon oxide delivering agent to —NH-CH2-CH2-NH— units is at least 0.5:1. The process makes it possible to obtain ethylene amines and derivatives thereof without using ammonia or metal-containing catalysts.

First claim

The invention claimed is:

1. A process for preparing polyethyleneamines of the formula NH2-(CH2-CH2-NH-)pH wherein p is at least 3, comprising the step of reacting monoethylene glycol with an amine-functional compound comprising at least two —NH— units of which at least one is selected from the group of primary amine groups and cyclic secondary amine groups, in the presence of a carbon oxide-delivering agent, the amine-functional compound comprising at least one —NH-CH2-CH2-NH— unit, wherein at least one —NH-CH2-CH2-NH-unit in the amine-functional compound is present in the form of a cyclic ethylene urea moiety of the formula

or a piperazine moiety of the formula

wherein
the molar ratio of amine-functional compound to monoethylene glycol is above 1.2:1 and
the molar ratio of carbon oxide-delivering agent to —NH-CH2-CH2-NH— in the amine-functional compound is at least 0.5:1,

wherein a —NH-CH2-CH2-NH— unit is a unit which can form an ethylene urea unit in the amine-functional compound, and
wherein the carbon oxide delivering agent is selected from the group of carbon dioxide, the CO adduct of monoethylene glycol selected from the group of cyclic ethylene carbonate and HO-CH2-CH2-O—C(O)—O-CH2-CH2-OH, and urea-derivatives of ethylene amine compounds.

2. The process according to claim 1 , wherein the carbon oxide-delivering agent is selected from the group of carbon dioxide and ethylene urea (EU) of the formula

3. The process according to claim 1 , wherein the molar ratio of amine-functional compound to monoethylene glycol is above 1.5:1.

4. The process according to claim 1 , wherein the molar ratio of carbon oxide-delivering agent to —NH-CH2-CH2-NH— units in the amine-functional compound is at least 0.5:1.

5. The process according to claim 4 , wherein the molar ratio of carbon oxide-delivering agent to —NH-CH2-CH2-NH— units in the amine-functional compound is between from 0.7:1 to 3:1.

6. The process according to claim 1 , wherein at least 50% of the CO is added in the form of the CO adduct of monoethylene glycol selected from the group of cyclic ethylene carbonate and HO-CH2-CH2-O—C(O)—O-CH2-CH2-OH, or in the form of urea-derivatives of ethylene amine compounds.

7. The process according to claim 1 , wherein the amine-functional compound comprises ethylene diamine (EDA) provided in the form of EDA, in the form of the urea derivative ethylene urea (EU) having the formula

or as a mixture thereof, and the reaction product comprises triethylenetetramine (TETA) of the formula NH2-(CH2-CH2-NH-)p-H wherein p is 3.

8. The process according to claim 1 , wherein the amine-functional compound comprises diethylene triamine (DETA) provided as DETA, as the urea adduct thereof (UDETA), or a mixture thereof, and the reaction product comprises pentaethylene hexamine (PEHA) of the formula NH2-(CH2-CH2-NH-)p-H wherein p is 5.

9. The process according to claim 1 , wherein the amine-functional compound comprises piperazine (PIP) and the reaction product comprises HN(CH2-CH2)2N-CH2-CH2-N(CH2-CH2)2NH.

10. The process according to claim 1 , wherein the reaction product is subjected to a hydrolysis reaction to convert the urea adducts present therein into ethylene amines.

11. The process according to claim 1 , wherein the molar ratio of amine-functional compound to monoethylene glycol is above 1.7:1.

12. The process according to claim 1 , wherein the molar ratio of amine-functional compound to monoethylene glycol is at most 5:1.

13. The process according to claim 1 , wherein the molar ratio of amine-functional compound to monoethylene glycol is at most 3:1.

14. The process according to claim 1 , wherein the molar ratio of carbon oxide-delivering agent to —NH-CH2-CH2-NH— units in the amine-functional compound is at least 1:1.

15. The process according to claim 1 , wherein the molar ratio of carbon oxide-delivering agent to —NH-CH2-CH2-NH— units in the amine-functional compound is at most 5:1.

16. The process according to claim 1 , wherein the molar ratio of carbon oxide-delivering agent to —NH-CH2-CH2-NH— units in the amine-functional compound is at most 3:1.

17. The process according to claim 4 , wherein the molar ratio of carbon oxide-delivering agent to —NH-CH2-CH2-NH— units in the amine-functional compound is between from 0.9:1 to 2:1.

18. The process according to claim 4 , wherein the molar ratio of carbon oxide-delivering agent to —NH-CH2-CH2-NH— units in the amine-functional compound is between from 1.1:1 to 1.75:1.

19. The process according to claim 1 , wherein at least 75% of the CO is added in the form of the CO adduct of monoethylene glycol selected from the group of cyclic ethylene carbonate and HO-CH2-CH2-O—C(O)—O-CH2-CH2-OH, or in the form of urea derivatives of ethylene amine compounds.

20. The process according to claim 1 , wherein at least 95% of the CO is added in the form of the CO adduct of monoethylene glycol selected from the group of cyclic ethylene carbonate and HO-CH2-CH2-O—C(O)—O-CH2-CH2-OH, or in the form of urea derivatives of ethylene amine compounds.

Assignees

• Nouryon Chemicals Int Bv

Inventors

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

Classifications

• C07C209/62

  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

• C07D233/36

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

• C07C209/16 Primary

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

• C07C211/14

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