Process for preparing ethyleneamine compounds

Patent metadata

Field	Value
Publication number	US-11072686-B2
Application number	US-201816638397-A
Country	US
Kind code	B2
Filing date	Aug 7, 2018
Priority date	Aug 11, 2017
Publication date	Jul 27, 2021
Grant date	Jul 27, 2021

Abstract

An integrated process for manufacturing polyethyleneamine compounds selected from the group of polyethyleneamines and hydroxyethylethyleneamines is provided. The process includes in an adduction step, providing a CO 2 adduct of a starting compound comprising a —NH—CH 2 —CH 2 —NH— moiety or a —NH—CH 2 —CH 2 —OH moiety, or HO—CH 2 —CH 2 —OH, in a reaction step reacting a hydroxy-functional compound selected from the group of ethanolamines and dihydroxyethane with an amine-functional compound, wherein at least part of the total of hydroxy-functional compounds and amine-functional compounds is provided in the form of a CO 2 adduct, to form CO 2 adduct of a product polyethyleneamine compound, in an elimination step converting CO 2 adduct of product polyethyleneamine compound to the corresponding product polyethylene amine compound, wherein a fraction comprising a recycle compound comprising a —NH—CH 2 —CH 2 —NH— moiety or a —NH—CH 2 —CH 2 —OH moiety, or HO—CH 2 —CH 2 —OH, or CO 2 adducts thereof, is provided from the end of the reaction step or the elimination step to the adduction step or to the reaction step, wherein the recycle compound has per molecule on average fewer of the total of —NH—CH 2 —CH 2 —NH— moieties and —NH—CH 2 —CH 2 —OH moieties than the product polyethyleneamine compound.

First claim

The invention claimed is:

1. An integrated process for manufacturing polyethyleneamine compounds selected from the group of polyethyleneamines and hydroxyethylethyleneamines comprising the steps of:
in an adduction step, providing a CO 2 adduct of a starting compound comprising a —NH—CH 2 —CH 2 —NH— moiety or a NH—CH 2 —CH 2 —OH moiety, or HO—CH 2 —CH 2 —OH,
in a reaction step, reacting a hydroxy-functional compound selected from the group of ethanolamines and dihydroxyethane with an amine-functional compound, wherein at least part of the total of hydroxy-functional compounds and amine-functional compounds is provided in the form of a CO 2 adduct, to form CO 2 adduct of a product polyethyleneamine compound,
in an elimination step, converting the CO 2 adduct of product polyethyleneamine compound to a corresponding product polyethylene amine compound,
wherein a fraction comprising a recycle compound comprising a NH—CH 2 —CH 2 —NH— moiety or a —NH—CH 2 —CH 2 —OH moiety, or HO—CH 2 —CH 2 —OH, or CO 2 adducts thereof, is provided from the end of the reaction step or the elimination step to the adduction step or to the reaction step,
wherein the recycle compound has per molecule on average fewer of the total of —NH—CH 2 —CH 2 —NH— moieties and —NH—CH 2 —CH 2 —OH moieties than the product polyethyleneamine compound.

2. The integrated process according to claim 1 , wherein the adduction step comprises an absorption step wherein gaseous CO 2 is reacted with a starting compound comprising a —NH—CH 2 —CH 2 —NH— moiety or a —NH—CH 2 —CH 2 —OH moiety, or HO—CH 2 —CH 2 —OH, to form a CO 2 adduct thereof.

3. The integrated process of claim 1 , wherein the adduction step comprises the step of reacting starting compound comprising —NH—CH 2 —CH 2 —NH— moiety or a —NH—CH 2 —CH 2 -0H moiety, or HO—CH 2 —CH 2 —OH with a carbon oxide delivering agent which can transfer a carbonyl group to the starting compounds, resulting in the formation of CO 2 adducts thereof.

4. The integrated process of claim 1 , wherein the elimination step comprises a desorption step in which the CO 2 adduct of product polyethyleneamine compound is reacted with water to form CO 2 and the corresponding product polyethylene amine compound.

5. The integrated process of claim 1 , wherein the elimination step comprises a caustic treatment step in which CO 2 adduct of product polyethyleneamine compound is reacted with an inorganic base, resulting in the formation of a product polyethyleneamine compound and a carbonate salt.

6. The integrated process of claim 1 , wherein the elimination step comprises a CO 2 transfer step, wherein the carbonyl group from the CO 2 adduct of the product polyethyleneamine compound is transferred to a compound having a —NH—CH 2 —CH 2 —NH— moiety or a NH—CH 2 —CH 2 —OH moiety, or HO—CH 2 —CH 2 —OH.

7. The integrated process of claim 1 , wherein the adduction step comprises an absorption step and the elimination step comprises a desorption step, and wherein CO 2 formed in the desorption step is provided at least in part to the absorption step.

8. The integrated process of claim 1 , wherein the adduction step comprises an absorption step and the elimination step comprises a desorption step, and wherein stripping gas withdrawn from the desorption step is subjected to a CO 2 removal step and recycled at least in part to the desorption step.

9. The integrated process according to claim 8 , wherein stripping gas containing CO 2 is removed from the desorption step and provided to absorption step, where CO 2 is absorbed from the CO 2 -containing stripping gas, and stripping gas from which CO 2 has been removed is withdrawn from the absorption step and provided to the desorption step.

10. The integrated process of claim 1 , wherein a separation step is provided after the elimination step, the separation step yielding a fraction comprising a recycle compound comprising a —NH—CH 2 —CH 2 —NH— moiety or a —NH—CH 2 —CH 2 —OH moiety, or HO—CH 2 —CH 2 —OH, or CO 2 adducts thereof, which fraction is provided in its entirety or in part to the adduction step or to the reaction step,
wherein the recycle compound has per molecule on average fewer of the total of —NH—CH 2 —CH 2 —NH— moieties and —NH—CH 2 —CH 2 —OH moieties than the product polyethyleneamine compound, the recycle compound comprising starting compounds and optionally intermediate compounds, the separation step further yielding a product fraction of product polyethyleneamine compounds.

11. The integrated process of claim 1 , wherein a separation step is provided after the reaction step and before the elimination step, the separation step yielding a fraction comprising a recycle compound comprising a —NH—CH 2 —CH 2 —NH— moiety or a —NH—CH 2 —CH 2 —OH moiety, or HO—CH 2 —CH 2 —OH, or CO 2 adducts thereof, which fraction is provided in its entirety or in part to the adduction step or to the reaction step, the separation step further yielding a fraction comprising CO 2 adduct of product polyethyleneamine compounds, which fraction is provided to the elimination step.

12. The integrated process of claim 1 , wherein the elimination step comprises a first elimination step and one or more further elimination steps, wherein the elimination steps are independently selected from the group consisting of:
a desorption step in which the CO 2 adduct of product polyethyleneamine compound is reacted with water to form CO 2 and the corresponding product polyethylene amine compound,
a caustic treatment step in which CO 2 adduct of product polyethyleneamine compound is reacted with an inorganic base, resulting in the formation of a product polyethyleneamine compound and a carbonate salt, and
a CO 2 transfer step, wherein the carbonyl group from the CO 2 adduct of the product polyethyleneamine compound is transferred to a compound having a —NH—CH 2 —CH 2 —NH— moiety or a NH—CH 2 —CH 2 —OH moiety, or HO—CH 2 —CH 2 —OH,
wherein the first elimination step converts part of the CO 2 adducts of polyethyleneamines present in the feed thereto into the polyethyleneamine compounds, while part of the CO 2 adducts of polyethyleneamines present in the feed to the first elimination step is not converted in the first elimination step, and is provided to a further elimination step.

13. The integrated process according to claim 12 , wherein the first elimination step is a desorption step or a CO 2 transfer step and the further elimination step is a desorption step or a caustic treatment step, wherein the steps are not the same.

14. The integrated process of claim 1 , wherein elimination step yields a product comprising polyethyleneamine compounds and CO 2 adducts of polyethyleneamine compounds, and this product is provided to a separation step where a fraction comprising CO 2 adducts of polyethyleneamine compounds is separated from the polyethyleneamine compounds, and processed in one or more of the following manners:
it is subjected at least in part to purification and further separation steps,
it is recycled at least in part to the elimination step,
it is provided at least in part to a further elimination step which is carried out under more stringent conditions than the first elimination step, and comprises, e.g., a treatment with an inorganic base,
it is provided at least in part to the reaction step.

15. The integrated process of claim 1 , wherein the starting materials are provided to the reaction step via one of the following methods:
the amine-compound is provided in its entirety or in part to the adduction step where it is converted into its CO 2 adduct, which is then provided to the reaction ste

Assignees

• Nouryon Chemicals Int Bv

Inventors

• Veneman Rens
• Ten Kate Antoon Jacob Berend
• Raaijmakers Michiel Jozef Thomas
• Jovic Slavisa
• Edvinsson Rolf Krister
• Kantzer Eike Nicolas
• Lake Karl Fredrik
• Ehlers Ina
• Van Dam Hendrik

Classifications

• Y02P20/10

  Process efficiency · CPC title

• C07C213/02 Primary

  by reactions involving the formation of amino groups from compounds containing hydroxy groups or etherified or esterified hydroxy groups · CPC title

• C08G73/0213 Primary

  Preparatory process · CPC title

• C07C213/08

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

• C07C209/68

  from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton · CPC title