The present invention relates to a process for making higher ethylene amines (EA), i.e. ethylene amines and derivatives (or precursors) thereof, like urea derivatives, that contain at least 3 ethylene units, by reacting an ethanolamine functional compound containing at least 2 ethylene units with an amine functional compound in the presence of a carbon oxide delivering agent. Ethylene amines consist of two or more nitrogen atoms linked by ethylene units. Ethylene amines can be present in the form of linear chains H2N(-C2H ₄ NH)p-H. For p= 1 ,2,3,4,... these are denoted EDA, DETA, L-TETA, L-TEPA,...

With three or more ethylene units it is also possible to create branched ethylene amines such as N(CH2CH ₂ NI-l2)3, TAEA. Two ad acent nitrogen atoms linked by two

ethylene units are called a piperazine ring Piperazine rings can be present in longer chains to produce the corresponding cyclic ethylene amines.

Two adjacent nitrogen atoms linked by one ethylene unit and one carbonyl moiety form a cyclic ethylene urea (EU). An ethylene amine (EA) in which two nitrogen atoms are

linked intramolecular by a carbonyl moiety - -is here referred to as an UEA.

Replacing the carbonyl bridge with two hydrogen atoms yields the corresponding ethylene amine. For example: EU ->EDA, UDETA ->DETA, UAEEA ->AEEA, UTETA ->L-TETA, UTEPA ->L-TEPA. Some higher amines host more than one carbonyl moiety, e.g. DUTETA the diurea of L-TETA. The carbonyl moiety may link nitrogen atoms on two separate molecules. For example H ₂ NC2H ₄ NH-CO-NHC2H ₄ NH2 and replacing the carbonyl moiety with two hydrogen atoms here yields two EDA. Each amine function in ethylene amines and ethylene ureas can be primary, secondary or tertiary. Furthermore, a secondary amine can be linear (linear secondary amines, LSA) or cyclic (cyclic secondary amine, CSA).

In the presence of any Bransted acid (such as water) ethylene amines (EA) can be protonated (EAH ⁺ ). If not otherwise stated the term amine in this document will include both the protonated and unprotonated form.

Some ethylene amines and urea derivatives thereof are shown below as an illustration. This can naturally be extended to include a.o. pentaamines, hexaamines and so on.

EDA EU

DETA UDETA

DUTETA

As to naming of the molecules, EDA stands for ethylenediamine, DETA for diethylenetriamine, TETA for triethylenetetraamine, TEPA for tetraethylenepentamine, PEHA for pentaethylenehexamine. When there is a single cyclic urea in the molecule this is indicated by adding a U in front of the name, i.e. UTETA means the cyclic urea of TETA, while when there are two cyclic ureas in the molecule this is indicated by DU, i.e. DUTETA means the cyclic diurea of TETA. If there is a number indicated for the U this refers to the amino group where the U group is located. There is one exception to this naming and that is that instead of UEDA the abbreviation EU is used, which stands for ethyleneurea. Furthermore, TAEA stands for trisaminoethylamine.

The manufacturing of ethylene amines is presently dominated by two routes. These are the reductive amination of MEA and the EDC route.

Reductive amination of MEA proceeds in the presence of a hydrogenation/dehydrogenation catalyst in an excess of ammonia. Next to the reductive amination of MEA to give EDA a number of side reactions including transamination produce a mixture of a large number of ethylene and ethanolamines. The output is dominated by mono and diethylene products (EDA, DETA, PIP and AEEA). Higher ethylene and ethanolamines are also formed but the mixture is complex and ineffective in producing high yields of the most important higher ethylene amines TETA and TEPA.

Several attempts to use transamination to produce ethylene amines with two or more ethylene units have been reported but seem limited to the diethylene compound DETA and have not been competitive to the EDC route described further below. See for example US 8,383,860 B2; US 8,188,318 B2; EP1654214B1 and US 4,568,745.

The EDC route is the substitution reaction of EDC (ethylene dichloride) with ammonia and/or another ethylene amine at elevated temperatures and pressures to form hydrochlorides which are then reacted with caustic to generate mixtures of ethylene amines and NaCI.

Today, the EDC-based process is the main process for producing higher polyethylene polyamines. By higher ethylene amines we refer to those containing three or more ethylene units. AEP is an example of a triamine. Higher amines usually exist in so- called technical mixtures. For example, there are several tetramines possible and their technical mixture which is referred to as TETA typically comprises L-TETA, TAEA, DAEP, PEEDA. Similarly TEPA refers to a mixture of pentaamines (linear, branched and piperazine containing). The EDC route apart from it being fully dependent on the use of ethylene dichloride which is toxic, highly flammable and carcinogenic, expensive, difficult to handle and therefore not always and everywhere available has as a disadvantage that it has a low selectivity towards specific higher ethylene amines, as it gives a mixture of many different polyethylene amines. Furthermore the EDC route results in the creation of a lot of NaCI which in embodiment results in corrosion and colored products thereby creating a need for additional purification steps like distillation or bleaching.

US 5,262,534 discloses a process for Ν,Ν,Ν trisubstituted nitrogen-containing compounds, for example by reacting a piperazine with a C02 synthon, such as certain oxazolidinones. Because oxazolidinones are a carbonic acid derivative of an ethanolamine, in all examples in the document the relative amount of carbonic acid derivative to ethylene amine is the same as the relative amount of ethanolamine to ethylene amine.

US 4,503,250 discloses the preparation of linear triethylene tetraamine L-TETA by reacting aminoethylethanolamine (AEEA) with EDA and a carbonic acid derivative (i.e. a carbon oxide delivering agent). It is said that the carbonic acid derivative can be a compound formed by earlier addition of an amine or alcohol to carbon dioxide. Though the document states in general that the components may be used in any amount, it suggests that the carbonic acid derivative functions as a catalyst and in all examples the carbonic acid derivative is used in a small amount relative to ethylene amine compound never to exceed the relative amount of ethanolamine to ethyleneamine compound. In the Examples, entry 5, AEEA is reacted with imidazolidinone (i.e a carbonic acid derivative of EDA) to give L-TETA, however in this Example the amount of carbon oxide delivering agent is very low, only around 0.3 equivalent on total amine compound (i.e. total EDA present in the imidazolidinone and as EDA) similarly low as the amount of ethanolamine-functional compound on amine-functional compound which is also 0.3 equivalent. For some embodiments it is indicated that the product mixture was only obtained after hydrolysis.

In pending PCT patent application PCT/EP2017/052948 a process is disclosed to prepare ethyleneamines of the formula NH2-(C2H ₄ -NH-) _P I-I 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 may be 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 ethanolamine-functional compound to amine-functional compound is at least 0.7:1 and the molar ratio of carbon oxide delivering agent to amine-functional compound is at least 0.05 : 1 . This document focuses at maximizing yield of ethyleneamines product. In a comparative Example 2 in this document the reaction of 3 moles EDA, 1 mole AEEA and 1.65 moles of urea at 280 deg C for 2 hours is disclosed, which reaction is disclaimed in this application, even though the selectivity in this reaction was not determined.

It has now been found that selectivity of the process to the ethylene amines products can be improved if the ratio ethanolamine-functional compound: amine-functional compound is relatively low and the carbon oxide delivering agent is dosed in a higher amount on amine-functional compound than the ethanolamine compound.

The selectivity of the process for the purpose of this application is defined as the molar selectivity of the ethanolamine reactant and/or its carbamate or urea derivative towards the higher ethyleneamines as prepared in the process (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 between two units -NH-C2H4-NH- a carbonyl moiety may be present). The selectivity can be calculated from the moles of higher ethyleneamines formed per mole of ethanolamine converted with respect to the ethanolamine used as a raw material in the process.

Even though the yield is not as high as possible such a process is very advantageous as much fewer side products are formed and unreacted starting materials can be easily recycled

The present invention now provides 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-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, by reacting an ethanolamine-functional compound OH-(C2H ₄ -NH-) _q H wherein q is at least 2, an amine- functional compound NH2-(C2H 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 between 0.05:1 and 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 is not the process of reacting 3 moles ethylenediamine (EDA) and 1 mole AEEA (aminoethylethanolamine) in the presence of 1.65 moles of urea at 280 deg C for 2 hours.

It was found that the selectivity of the reaction towards producing specific higher ethylene amines increases when working within the molar ratio ranges of the present invention, wherein the selectively obtained specific higher ethyleneamine product is the product wherein the value of p is the sum of q and r, including its urea derivatives. It should be noted that US 4,387,249 discloses a selective process to manufacture diethylene triamine by reacting monoethanolamine, ethylenediamine and urea. The document says that the most preferred mole ratio of the reactants ethylenediamine to urea to ethanolamine is about 3/1 .25/1. Monoethanolamine is an ethanolamine- functional compound OH-(C2H ₄ -NH-) _q H wherein q is 1 and thereby outside the scope of the present invention. Also monoethanolamine is in reactions as the one covered by the present invention not comparable with the ethanolamines wherein q is at least 2 due to the propensity of monoethanolamine to form a carbamate rather than a urea which is the case for ethanolamines where q is 2 or higher. For example, contacting a carbon oxide delivering agent with monoethanolamine and aminoethylethanolamine, respectively, at a suitable reaction temperature will produce CMEA and UAEEA, respectively, as can be found in US 3,133,932 that discloses the formation of the cyclic MEA-derived carbamate CMEA and in W097/49686 that discloses in Example L the formation of the cyclic AEEA-derived urea UAEEA. The former is a cyclic carbamate and the latter is a cyclic urea and they display substantially different chemical reactivities and hence kinetic and thermodynamic profiles as intermediates such as in the present invention. As a skilled person will understand, the reactivity of the separate reactants largely influences the selectivity towards such reactants. All the above makes that the the reaction as found for monoethanolamine does not have predictive value for how bigger ethanolamines will react. This can also be seen below where the optimum for the ratio of carbon oxide delivering agent to other reactants is given. This clearly deviates from the optimum defined in US 4,387,249 for using MEA.

Preferably, 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. In a more preferred embodiment the molar ratio of carbon oxide delivering agent to amine-functional compound is at least 20% higher than the molar ratio of ethanolamine-functional compound to amine-functional compound. In even more preferred embodiments when starting from amines and ethanolamines that are bigger in size and that contain 3 or more ethylene units, 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. The molar ratio of carbon oxide delivering agent to amine- functional compound in embodiments can be up to 500% higher than the molar ratio of ethanolamine-functional compound to amine-functional compound, but preferably is up to 300% higher, even more preferably 200% higher. In another preferred embodiment the molar ratio of ethanolamine-functional compound to amine-functional compound is between 0.1 :1 and 0.5:1 , even more preferably between 0.2:1 and 0.4:1. It should be noted that compounds exist that contain more than one carbonyl group that can be released from the molecule for transfer to the ethanolamine-functional compound, such as for example DUTETA. When determining the molar ratio for such compounds there should be an adjustment for the molar amount of carbon oxide they can release for transfer to the ethanolamine-functional compound. Accordingly, 1 mole of DUTETA should be considered 2 moles of carbon oxide delivering agent.

The molar amount of carbon oxide delivering agent on amine-functional compound is determined by the reactants in the process, independent of the dosing regime used for the reactants.

The reaction mixture is characterized by containing as reactants ethanolamine- functional compound, amine-functional compound and carbon oxide delivering agent and can be roughly represented by below non-limiting scheme.

Scheme I: Amine functional compound is a primary amine

T Addition of CO to the ethanolamine to form the 2-oxazolidinone ring

II Chain extension by ring opening by primary amine

III Removal of carbonyl group to form the ethylene amine

IV Intramolecular rearrangement of carbonyl group

V Hypothetical direct uncatalyzed amination

A number of reactions take place in parallel when heating a mixture of a carbonyl source, an ethanolamine-functional compound and an amine-functional compound. Without being bound to theory this can be summarized in two main reaction steps each composed of multiple sub steps: 1 ) the activation of the alcohol function (A) by the carbonyl group, the oxazolidinone (B) is assumed to be an intermediate (for the embodiments of this invention mainly in theory, because the carbonyl unit will substantially end up as a cyclic urea unit in the R1 group), 2) the activated alcohol function is replaced by an amine (C) to give a chain extended primary addition product (D). In the presence of ammonia a conversion of the alcohol function to an amine function without giving a chain extension can take place as well. The product (D) may undergo further reaction leading to secondary CO containing products as illustrated by reaction IV and product (F). Such products include but are not limited to cyclic ethylene urea derivatives but include all kinds of CO containing amines as for example illustrated in below examples of CO delivering agents. Optionally the CO groups can be removed leading to the formation of an ethylene amine (E).

The ethanolamine-functional compound is a compound containing one hydroxyl group linked via an ethylene to an amine group that optionally may be present as its carbamate equivalent. Generally the ethanolamine-functional compound is of the following formula

Where R is an ethyleneamine group of the formula -(C2H ₄ -N) _q-1 -H (q being at least 2 as

o defined above) in which optionally a cyclic urea unit -may be present.

Examples of ethanolamine functional compounds include

AEEA CAEEA

HE-DETA CHE-DETA CMEA-UDETA

As to naming convention, AEEA stands for aminoethylethanolamine (also referred to as hydroxyethylethylenediamine), HE-DETA for hydroxyethyldiethylenetriamine, and from there on HE-TETA for hydroxyethyl triethylenetetramine etc. By using the letter C it is indicated that a cyclic carbamate ring is present in the molecule.

The carbon oxide delivering agent is a compound containing a carbonyl moiety that can be transferred to an ethanolamine functional compound leading to the formation of a cyclic carbamate, such as CAEEA (the cyclic carbamate of aminoethyl ethanolamine) or that can be transferred to an ethylene amine (EA) leading to the formation of the corresponding cyclic ethylene urea (UEA). Next to cyclic compounds linear carbamates and ureas may form as well.

Carbon oxide delivering agents within the scope of the present invention include organic compounds in which a carbonyl moiety is available for being transferred as described above. Organic compounds in which a carbonyl moiety is available for being transferred include carbon dioxide, urea, linear and cyclic alkylene ureas, especially cyclic ureas, mono or di-substituted alkylene ureas, alkyl and dialkyl ureas, linear and cyclic carbamates, especially cyclic carbamates, organic carbonates and derivatives or precursors thereof. Such derivatives or precursors may for example include ionic compounds such as carbonate or bicarbonate salts, carbamic acids and associated salts, that can be converted, in some embodiments in situ in the process of the invention, into their non-ionic counterparts, for example into linear and cyclic carbamate or urea compounds. When such ionic compounds are used in the present invention, they are organic hydrocarbon-based carbonate, bicarbonate or carbamate salts. Preferably the CO delivering agent is C0 _2, urea, or an organic compound wherein alkylene is ethylene, such as a cyclic urea of an ethylene amine, or cyclic carbamate of an ethanolamine, ethylene carbonate, more preferably the carbon oxide delivering agent is at least partly added as carbon dioxide or urea. The carbon oxide delivering agent can be present in the process in the same molecule as the amine functional or the ethanolamine functional compound by using the aforementioned urea or carbamate compounds.

Examples of carbon oxide delivering agents include

EDA carbamate Zwitterion EDA carbamate

EDA dicarbamate

EDA bicarbonate EDA carbonate

DAEC AE AE carbamate diaminoethyl carbonate

O O

H,N„

HN NH A ,ΝΗ

\_

EU DAEU

CAEEA UAEEA

O

,NH ₉

HN N'

\_/

UDETA

CHE-DETA U1TETA DUTETA In the above drawing CAEEA again stands for the carbamate of aminoethylethanolamine, UDETA for the urea of diethylene triamine, DAEU stands for diaminoethyl urea, AE AE carbamate stands for amino ethyl aminoethanol carbamate, CHE-DETA stands for the carbamate of hydroxyethyldiethylene triamine, U 1 TETA stands for the terminal urea of triethylene tetramine, and DUTETA stands for the 1 ,3- diurea of triethylene tetramine.

The carbon oxide delivering agent is most preferably added to the reaction in the form of carbon dioxide, the carbamate derivative of the ethanolamine-functional compound or the urea derivative of the amine-functional compound, or a combination of these.

Heating a suitable mixture of an ethanolamine, an amine that is not tertiary and a carbon oxide delivering agent to a relatively high temperature provides a way to produce a higher amine and CO containing derivative thereof that can serve as a carbon oxide delivering agent.

The amine-functional compound is a compound containing one or more amine groups, preferably at least two amine groups, and no alcohol groups. In a preferred embodiment the amine-functional compound is a compound containing at least two amine groups. Even more preferred the amine-functional compound contains at least two primary amine groups, and optionally more amine groups that may be primary, secondary and/or tertiary amines wherein the amine groups within the compound are linked to one another via ethylene groups, and optionally some by a carbonyl moiety (to give a urea unit in the amine functional compound). It should be noted that tertiary amines are only present in an amine of the formula NH ₂ -(C2H ₄ -NH- )pH if there is piperazine unit in the compound.

In another preferred embodiment the ethanolamine-functional compound and the carbon oxide delivering agent are at least partly added as one compound by using a carbamate adduct and/or the amine-functional compound and the carbon oxide delivering agent are at least partly added as one compound by using an urea adduct. A carbamate compound for the present invention is not considered an amine-functional compound, like an ethanolamine-functional compound is not considered an amine- functional compound.

In a more preferred embodiment the ethanolamine-functional compound is AEEA, UAEEA, CAEEA or a mixture thereof and the amine-functional compound EDA, EU or a mixture thereof.

In an embodiment the amine-functional compound and/or the ethanolamine-functional compound are obtained directly or indirectly from an amine production process as described above, such as for example a reductive amination process or EDC process.

For the avoidance of doubt, in the process of the present invention also derivatives of ethyelene amines are covered as products, these derivatives are the compounds 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. It should be noted that compounds wherein piperazine units are present are usually only obtained if such piperazine units were also present in one of the reactants. This is not the case for products where a cyclic ethylene urea unit or bridging carbonyl moiety is present, this unit and/or moiety may result from the reaction between any carbon oxide delivering agent and one of an ethanolamine-functional compound, amine-functional compound or obtained ethylene amine product.

The product mixture can be further processed or fractionated into several products that each independently are either pure compounds or mixture of compounds, some of which may be recycled. The process of the present invention can be done with or without any additional liquid present. If a liquid is added to the reaction system, the liquid preferably is a polar liquid, such as an alcohol or water. Doing the process of the present invention in the presence of water as a liquid or without any additional liquid is preferred.

If an of the ethanolamine-functional compound or amine-functional compound preferably the reaction is performed in a liquid wherein the liquid comprises water as then both the yield and selectivity can be increased. The reactants do not count as part of the above liquid. Hence, even if one or more of the ethanolamine-functional compound, amine-functional compound or carbon oxide delivering agent are liquid at the reaction conditions, these are not considered part of the above liquid in which the process of the invention is performed.

In a preferred embodiment when having compounds with piperazine units in the process of the invention, the liquid contains at least 50 wt-% of water up to 100 wt-% of water, wherein more preferably the remaining up to 50 wt-% is a polar liquid that mixes homogenously with water at the conditions employed during the process of the invention. Even more preferably the liquid contains at least 75 wt-% of water, yet more preferably at least 90 wt-%, most preferably at least 95-wt% on total liquid weight.

The reactor employed can be any suitable reactor including continuously stirred tank reactor, pipeline reactor, tubular or multi-tubular reactor. The reactor may be adiabatic or equipped with external or internal heating devices. Feed may be single point or split into multiple points. It can consist of multiple stages with inter-stage heat exchange.

The process is preferably performed at a temperature of at least 100°C. The temperature should preferably be lower than 400°C. More preferably the temperature is between 200 and 360 °C. Even more preferably the temperature is between 230 and 340 °C. Most preferably the temperature is between 250 and 310 °C. The reaction time during the process is in an embodiment between 5 minutes and 15 hours, preferably between 10 minutes and 10 hours, more preferably between 15 minutes and 6 hours. The process can be carried out in one or multiple batch reactors, possibly in fed-batch operation, and/or in a continuously operating system in one reactor or in a cascade of continuous flow reactors, optionally with multiple feeding points. The reaction and separation can be performed in separate steps or at least partially simultaneously. The reaction and separation can involve multiple reaction steps with separation steps in between.

In the large-scale production of chemicals it is preferred to employ a continuous process. The continuous process may be, for example, a single-pass or a recycle process. In a single-pass process, one or more of the reagents pass through the process equipment once, and then the resulting effluent from the reactor is sent for purification or further processing.

The person skilled in the art is capable of selecting the proper reactor and separation unit scheme by determining the overall yield, energy consumption and waste production.

In yet another more preferred embodiment, mixtures of several alcohol and amines can be used that may amongst other contain aminoethylethanolamine (AEEA) and ethylenediamine (EDA), and/or DETA (diethylenetriamine) in combination with further amine-functional compounds and ethanolamine-functional compounds and that are reacted with urea or C02 as a carbon oxide delivering agent to form higher ethylene polyamines, mainly triethylenetetramine (TETA) and tetraethylenepentamine (TEPA):

Examples

For a reaction mixture containing a single ethanol amine and its urea derivative starting mixture, a general selectivity can be calculated from: mol (U)ethylene amines formed

Selectivity =

mol U)ethanolamine at start— mol U)ethanolamine remaining

Here, (U)ethylene amine stands for ethylene amine and its urea derivative and (U)ethanol amine stands for ethanol amine and its urea derivative. For example for the reaction mixture starting with AEEA, EDA and carbon oxide delivering agent, the selectivity is calculated from: mol (D)(U)TETA formed

Selectivity

mol (U)AEEA at start— mol (U)AEEA remaining

Here, (D)(U)TETA stands for tri-ethylene tetra-amine and its mono- and di-urea derivatives and (U)AEEA stands for amino ethyl ethanol amine and its urea derivative.

For a reaction mixture containing more than one ethanol amine and its urea derivative in the starting mixture, a general selectivity can be calculated from: mol (U)EA formed

Selectivity

mol (U)ethanolamines at start— mol (U)ethanolamines remaining

With the ethanolamines and their urea derivatives exclusively the types that were initially present, and not any newly formed (higher) ethanol amines.

Abbreviations used in Examples:

CO = carbon oxide delivering agent

OH = ethanolamine-functional compound

Amine = amine-functional compound

OH/amine is the molar ratio of ethanolamine-functional compound to amine-functional compound

CO/amine is the molar ratio of carbon oxide delivering agent to amine-functional compound

CO/OH is the molar ratio of carbon oxide delivering agent to ethanolamine-functional compound Example 1

Reaction of UAEEA with EDA and EU. The CO/Amine ratio was varied between 1, 0.6, and 0.2. The OH/amine ratio was kept at 0.3.

The urea derivative of aminoethylethanolamine (UAEEA), ethyleneurea (EU, the urea derivative of ethylenediamine), ethylenediamine (EDA) were added to a microwave vial in the respective amounts as indicated in Table 1 . The vials were capped, flushed with N ₂ , and heated at 285°C for 4 h. The samples were then allowed to cool and the content was analyzed by gas chromatography coupled with a flame ionization detector (GC-FID).

Table 1

AII GC FID data in wt.%

Sum (U)TETA denotes the sum of L-TETA and urea adducts thereof In the Table 1 it can be seen that working at the OH/amine ratio of the present invention and a CO/amine ratio that is higher than the OH/amine ratio is favorable for selectivity and also that having the CO/amine at least 50% higher than the OH/amine ratio further improves the selectivity.

Example 2

Reaction of UAEEA with EDA and EL). The CO/Amine ratio was kept at 1. The OH/amine ratio was varied at 0.3, 0.5 and 1.1.

The urea derivative of aminoethylethanolamine (UAEEA), ethyleneurea (EU, the urea derivative of ethylenediamine), ethylenediamine (EDA) were added to a microwave vial in the respective amounts as indicated in Table 2. The vials were capped, flushed with N ₂ , and heated at 285 °C for 4 h. The samples were then allowed to cool and the content was analyzed by gas chromatography coupled with a flame ionization detector (GC-FID).

Table 2

Example 2A 2B 2C (comparative)

Reactants AEEA/EU AEEA/EU AEEA/EU

CO/amine 1 1 1

OH/amine 0.3 0.5 1 .1

CO/amine 3.33 2 0.91 reactant amounts in g 2.7:7.3 3.8:6.2 5.7:4.3 molar ratio of reactants 1 :3.33 1 :2 1 :0.91

Reaction time in hours 4 4 4

EDA 16 18 14

AEEA 1 2 10

EU 36 15 3

UAEEA 16 16 18

Sum (U)TETA 25 36 32

Molar conversion of

(U)AEEA 0.52 0.61 0.58 Molar selectivity of

(U)AEEA to (U)TETA 0.94 0.85 0.56

All GC FID data in wt.%

Sum (U)TETA denotes the sum of L-TETA and urea adducts thereof

It is clearly demonstrated that the OH/amine ratio has an influence on the molar selectivity towards higher ethylene amines..

Example 3

Reaction of UAEEA with EDA and EU. The CO/OH ratio was varied at 0.75 and 1.5.

The OH/amine ratio was varied at 0.5 and 0.6.

The urea derivative of aminoethylethanolamine (UAEEA), ethyleneurea (EU, the urea derivative of ethylenediamine), ethylenediamine (EDA) were added to a microwave vial in the respective amounts as indicated in Table 3. The vials were capped, flushed with N ₂ , and heated at 285 °C for 3.5 h. The samples were then allowed to cool and the content was analyzed by gas chromatography coupled with a flame ionization detector (GC-FID).

Table 3

Example 3A 3B 3C 3D

(comparative) (comparative) reactants AEEA/UAEEA/ AEEA/UAEEA/ AEEA/EU/EDA AEEA/EU/EDA

EU/EDA EU/EDA

CO/amine 0.75 0.9 0.375 0.45

OH/amine 0.5 0.6 0.5 0.6

CO/OH 1 .5 1 .5 0.75 0.75 reactant amounts in g 2.57:1 .68:3.88: 2.85:1.78:4.13: 4.27:2.65:3.08 4.65:2.28:2.47

1 .86 1 .24

molar ratio of reactants 1 :0.5:1 .75:1 .25 1 :0.5:1 .75:0.75 1 :0.75:1.25 1 :0.75:0.92

Reaction time in hours 3.5 3.5 3.5 3.5

EDA 23 17 40 35

AEEA 3 3 14 13

EU 13 1 1 5 4 UAEEA 14 17 17 18

Sum (U)TETA 28 30 1 1 12

Molar conversion of

(U)AEEA 0.63 0.62 0.36 0.41

Molar selectivity of

(U)AEEA to (U)TETA 0.64 0.65 0.44 0.39

All GC FID data in wt.%

Sum (U)TETA denotes the sum of L-TETA and urea adducts thereof

Table 3 demonstrates that when having the OH/amine ratio between 0.05:1 and 0.7:1 , selectivity improves when the CO:amine ratio is higher than the OH:amine ratio. The yield of the desired (U)TETA product is much higher when operating at this higher CO/amine ratio. Experiments 3A and 3B have a much higher yield and selectivity towards (U)TETA's as compared to experiments 3C and 3D. Example 4

Reaction of UAEEA with EDA and EU CO/Amine = 0.875 and OH/amine = 0.25

The urea derivative of aminoethylethanolamine (UAEEA), ethyleneurea (EU, the urea derivative of ethylenediamine), ethylenediamine (EDA) were added to a microwave vial in the respective amounts as indicated in Table 4. The vials were capped, flushed with N ₂ , and heated at 280 °C for 2.5 and 5h, respectively. The samples were then allowed to cool and the content was analyzed by gas chromatography coupled with a flame ionization detector (GC-FID).

Table 4

Example 4a 4b

reactants UAEEA/EU/EDA UAEEA/EU/EDA

CO/amine 0.875 0.875

OH/amine 0.25 0.25

CO/OH 3.5 3.5 reactant amounts in g 0.45/0.775/0.31 1 0.45/0.775/0.31 1 molar ratio of reactants 1 :2.5:1.5 1 :2.5:1.5

Reaction time in hours 2.5 5 EDA 17.3 17.2

AEEA 0.7 0.4

EU 36.1 32.1

UAEEA 14.2 8.1

Sum (U)TETA 20.1 27.3

Molar conversion of (U)AEEA 0.49 0.71

Molar selectivity of (U)AEEA to

(U)TETA 0.99 0.98

All GC FID data in wt.%

Sum (U)TETA denotes the sum of L-TETA and urea adducts thereof

Molar selectivities above 0.95 were achieved by using a reaction mixture where the ratio ethanolamine-functional compound: amine-functional compound is in the range of the invention and the carbon oxide delivering agent is dosed in a higher amount on amine-functional compound than the ethanolamine compound is dosed on the amine- functional compound. Example 5

Reaction of UAEEA with EDA and EU CO/amine = 1.07 and OH/amine = 0.33

The urea derivative of aminoethylethanolamine (UAEEA), ethyleneurea (EU, the urea derivative of ethylenediamine), ethylenediamine (EDA) were added to a microwave vial in the respective amounts as indicated in Table 5. The vials were capped, flushed with N ₂ , and heated at 280 °C for 5 and 10h, respectively. The samples were then allowed to cool and the content was analyzed by GC-FID.

Table 5

Example 5a 5b

reactants UAEEA/EU/EDA UAEEA/EU/EDA

CO/amine 1.07 1.07

OH/amine 0.33 0.33

CO/OH 3.2 3.2 reactant amounts in g 0.45/0.682/0.166 0.45/0.682/0.166 molar ratio of reactants 1 :2.2:0.8 1 :2.2:0.8

Reaction time in hours 5 10

EDA 12.9 1 1.8

AEEA 0.3 n.d.

EU 31.1 25.6

UAEEA 12.1 3.9

Sum (U)TETA 25.9 32.5

Molar conversion of (U)AEEA 0.64 0.89

Molar selectivity of (U)AEEA

to (U)TETA 0.88 0.81

All GC-FID data in wt.%

Sum (U)TETA denotes the sum of L-TETA and urea adducts thereof

Molar selectivities above 0.8 were achieved by using a reaction mixture where the ratio ethanolamine-functional compound: amine-functional compound is relatively low and the carbon oxide delivering agent is dosed in a higher amount on amine-functional compound than the ethanolamine compound is dosed on the amine-functional compound. Comparison with Example 4 shows that both the CO/Amine and OH/amine ratio's are relevant for obtaining high selectivities.

Comparative Example 6

Reaction of AEEA with EDA and EU CO/amine = 0.75 and OH/amine = 1

The aminoethylethanolamine (AEEA), ethyleneurea (EU, the urea derivative of ethylenediamine), ethylenediamine (EDA) were added to a pressure vessel in the respective amounts as indicated in Table 6. The reaction vessel was closed, flushed with N ₂ and heated to 270 °C for 5h. The sample was then allowed to cool and the content was analyzed by GC-FID.

Table 6

Example 6

reactants AEEA/EU/EDA

CO/amine 0.75

OH/amine 1 CO/OH 0.75

reactant amounts in g 10/6.2/1 .44

molar ratio of reactants 1 :0.75:0.25

Reaction time in hours 2.5

EDA 15.5

AEEA 8.7

EU 3.3

UAEEA 12.7

Sum (U)TETA 28.1

Molar conversion of (U)AEEA 0.67

Molar selectivity of (U)AEEA to

(U)TETA 0.45

All GC-FID data in wt.%

Sum (U)TETA denotes the sum of L-TETA and urea adducts thereof

Conclusion: Molar selectivities of 0.45 were achieved by using a reaction mixture where the ratio ethanolamine-functional compound : amine-functional compound is outside the range of the invention and higher than the carbon oxide delivering agent : amine-functional compound ratio. The Example clearly shows that the selectivity of AEEA towards L-TETA and urea adducts thereof is much lower than for the Examples where the carbon oxide delivering agent : amine functional compound ratio is higher than the ethanolamine-function compound : amine-functional compound ratio.

Example 7 Reaction of UAEEA with DETA and UDETA CO/amine = 1 and 1.33, OH/amine = 0.33 The urea derivative of aminoethylethanolamine (UAEEA) and the urea derivative of diethylenetriamine (UDETA) and diethylenetriamine (DETA) were added to a pressure vessel in the respective amounts as indicated in Table 7. The pressure vessel was closed, flushed with N ₂ , and heated at for 4h at the reaction temperature as shown in Table 7. The sample was then allowed to cool and the content was analyzed by GC- FID. Table 7

All GC-FID data in wt.%

Sum (U)TEPA denotes the sum of L-TEPA and urea adducts thereof

Conclusion: molar selectivities of above 0.6 were achieved by using a reaction mixture where the ratio ethanolamine-functional compound: amine-functional compound is in the range of the invention and the carbon oxide delivering agent is dosed in a higher amount on amine-functional compound than the ethanolamine compound is dosed on the amine-functional compound.

The product mixture obtained in Example 7b was treated with a sodium hydroxide solution after which the amount of TEPA (i.e. tetraethylenepentamine without cyclic ethylene urea unit) on total (U)TEPA was increased. Comparative Example 8

Reaction of UAEEA with DETA CO/amine = 7, OH/amine = 7 The urea derivative of aminoethylethanolamine (UAEEA) and diethylenetriamine (DETA) were added to a pressure vessel in the respective amounts as indicated in Table 8. The pressure vessel was closed, flushed with N ₂ , and heated at 270 °C for 5h. The sample was then allowed to cool and the content was analyzed by GC-FID.

Table 8

All GC-FID data in wt.%

Sum (U)TEPA denotes the sum of L-TEPA and urea adducts thereof

A molar selectivity of only 0.1 was achieved by using a reaction mixture where the ratio ethanolamine-functional compound : amine-functional compound is higher than 0.7:1 and moreover equal to the carbon oxide delivering agent : amine-functional compound ratio. The example clearly shows that the selectivity of AEEA towards L-TEPA and urea adducts thereof is much lower than in previous example where the carbon oxide delivering agent : amine functional compound ratio is higher than the ethanolamine- function compound : amine-functional compound ratio. Example 9

Reaction of AEEA with EDA in the presence of CO?- CO/amine = 1 and OH/amine = 05

The aminoethylethanolamine (AEEA), ethylenediamine (EDA) and carbon dioxide gas (C0 ₂ ) were added to a high pressure autoclave in the respective amounts as indicated in Table 9. Before addition of the C0 ₂ , the autoclaves were filled with the EDA and AEEA, flushed with N ₂ . The C0 ₂ was added after pre-heating the amine mixture to a temperature of 130 °C. The mixture was heated to 280 °C with a heating rate of 5 °C/min. After reaching a temperature of 280 °C, the reaction mixture was kept at the setpoint temperature for 2h and 4.5h, respectively. The samples were then allowed to cool and the content was analyzed by GC-FID. Table 9

All GC-FID data in wt.%

Sum (U)TETA denotes the sum of L-TETA and urea adducts thereof Conclusion: molar selectivities of above 0.7 were achieved by using a reaction mixture where the ratio ethanolamine-functional compound: amine-functional compound is in the claimed range, the carbon oxide delivering agent is dosed as C0 ₂ in the gas phase and is dosed in a higher amount on amine-functional compound than the ethanolamine compound is dosed on the amine-functional compound.