The invention pertains to the manufacture of ethyleneamine compounds selected from the group of ethyleneamines, and hydroxyethylethyleneamines.

Ethyleneamine compounds, more specifically ethyleneamines and hydroxyethylethyleneamines, are useful in many applications.

Ethyleneamines consist of two or more nitrogen atoms linked by ethylene units. Ethyleneamines can be present in the form of linear chains H2N(-CH2-CH2-NH)p-H. For p = 1 ,2,3,4,... this gives, respectively, ethylenediamine (EDA), diethylenetriamine (DETA), linear triethylenetetramine (L-TETA), and linear tetraethylenepentamine (L-TEPA). As will be clear, this range can be extended. With three or more ethylene units it is also possible to create branched ethyleneamines such as N(CH2-CH2-NH2)3, trisaminoethylamine (TAEA). Two adjacent nitrogen atoms can be connected by two ethylene units to form a piperazine ring. Piperazine rings can be present in longer chains to produce the corresponding piperazine-ring- containing ethyleneamines.

Ethyleneamines, in particular diethylenetriamine (DETA) and further higher ethyleneamines such as linear triethylenetetramine (L-TETA) and linear tetraethylenepentamine (L-TEPA), are attractive products from a commercial point of view. In particular, the interest in higher ethyleneamines is increasing as these compounds have numerous commercial applications, e.g., as starting materials for, or use in, asphalt additives, corrosion inhibitors, epoxy curing agents, fabric softeners, fuel additives, hydrocarbon purification, ion exchange resins, lube oil additives, paper wet-strength resins, petroleum production chemicals, solvents, synthetic resins such as amide resins, mineral processing aids and interface-active substances (surfactants).

Hydroxyethylethyleneamines find application in chemical processes, as solvent or as reactant. For example, aminoethylethanolamine or AEEA of the formula H2N-CH2-CH2-NH-CH2-CH2- OH is an organic base used in the industrial manufacture of fuel and oil additives, chelating agents, and surfactants. Chain-extended ethanolamines, e.g., monoethanolamine compounds of the formula H2N-(CH2-CH2-NH)q-CH2-CH2-OH, wherein q is 2 or higher, are interesting intermediates for various types of organic synthesis, e.g., the manufacturing of esters of carboxylic acids. They can also be used in, for example, the formation of synthetic resins, as surfactants, for the production of emulsifiers, in fabric softeners, and as epoxy curing agents. Today, the EDC-based process is the main process for producing higher ethyleneamines, defined for the purposes of the present specification as ethyleneamines with at least two ethylene moieties. The EDC route is the substitution reaction of EDC (ethylenedichloride) with ammonia and/or an ethyleneamine at elevated temperatures and pressures to form hydrochloride salts of ethyleneamines which are then reacted with caustic to generate mixtures of ethyleneamines and NaCI. The EDC route has its disadvantages. It is dependent on the use of ethylenedichloride which is expensive, difficult to handle, and connected to HSE issues. Additionally, the EDC route gives a mixture of many different ethyleneamines. Nevertheless, as demonstrated by its widespread use, it remains an attractive process for manufacturing ethyleneamines.

In view of the fluctuating market conditions for ethyleneamine compounds and for the starting materials used in their manufacture there is need in the art for a process which allows flexibility in the products produced, and in the starting materials used. There is also need in the art for a process which combines flexibility for the starting materials and products used with efficient use of apparatus and efficient processing of waste streams. The present invention provides a process which addresses these issues.

The invention pertains to a process for manufacturing ethyleneamine compounds selected from the group of ethyleneamines and hydroxyethylethyleneamines wherein the process comprises two reaction sequences,

the first reaction sequence comprising the steps of

- in an adduction step providing a C02 adduct of a starting compound comprising a -NH-CH2- CH2-NH- moiety or a -NH-CH2-CH2-OH moiety, or HO-CH2-CH2-OH,

- in a chain-extension step reacting a hydroxy-functional compound selected from ethanolamines and dihydroxyethane with an ethyleneamine compound, wherein at least part of the total of hydroxy-functional compounds and ethyleneamine compound is provided in the form of a C02 adduct, to form a C02 adduct of a chain-extended ethyleneamine compound,

- in an elimination step converting a C02 adduct of a chain-extended ethyleneamine compound to the corresponding product ethyleneamine compound by removal of the carbonyl group, and

the second reaction sequence comprising the steps of

- in an amination step reacting monoethanolamine with ammonia in the presence of hydrogen and an amination catalyst to form a reaction mixture comprising ethylenediamine, - in a separation step separating the reaction mixture derived from the amination step into at least two fractions,

with the first reaction sequence and the second reaction sequence being connected in that at least one of the following takes place:

- effluent from a step in the first reaction sequence is provided as starting material to a step in the second reaction sequence,

- effluent from a step in the second reaction sequence is provided as starting material to a step in the first reaction sequence,

- a step of the first reaction sequence and a step of the second reaction sequence are combined, or

- effluent from a step in the first reaction sequence is combined with effluent from a step in the second reaction sequence.

The process according to the invention uses two connected reaction sequences for the manufacture of ethyleneamine compounds. Each reaction sequence has its own advantages. The process of the first reaction sequence allows the manufacture of high molecular weight ethyleneamine compounds, in particular straight-chain compounds. The process of the second reaction sequence allows the manufacture in an efficient manner of a reaction product comprising a mixture of many different ethyleneamine compounds, some of which are interesting as products in themselves while others may be more attractive as starting materials for the manufacture of higher ethyleneamine compounds. As will be discussed in more detail below, the process according to the invention allows for flexibility in starting materials used and products produced, and an efficient use of apparatus.

A particular advantage of the process according to the invention is that it makes it possible to produce a wide range of ethyleneamine products from ammonia and monoethanolamine. In one embodiment, ethylenediamine formed in the second reaction sequence from monoethanolamine and ammonia is provided to the first reaction sequence, where it is reacted with monoethanolamine. In this manner, a variety of products can be obtained from widely available starting materials. In a further embodiment, the monoethanolamine provided to either or both reaction sequences is obtained from reacting ethyleneoxide with ammonia, allowing the use of even more widely available starting materials.

A further advantage is that ethanolamine compounds such as aminoethylethanolamine which may be formed as a side product in the second reaction sequence may be processed via the first reaction sequence, resulting in an efficient use of available equipment.

A further advantage is that specific ethyleneamine compounds containing piperazine rings, e.g., piperazinoethyl ethylenediamine (PEEDA), diaminoethylpiperazine, and the piperazine- ring-containing penta- and hexaethyleneamines, can be obtained by providing cyclics such as piperazine and aminoethylpiperazine manufactured in the second reaction sequence to the first reaction sequence.

Further advantages of the present invention and specific embodiments thereof will become apparent from the further specification.

The invention will be elucidated with reference to the following figures, without being limited thereto or thereby.

Figure 1 illustrates a first embodiment of the process according to the invention.

Figures 2, 2a, and 2b illustrate further embodiments of the process according to the invention. Figure 3 illustrates a further embodiment of the process according to the invention.

Figure 4 illustrates a further embodiment of the process according to the invention.

Figure 5 illustrates a further embodiment of the process according to the invention.

In the following, the two individual reaction sequences will be discussed. Then, the various ways in which the reaction sequences can be connected will be discussed.

The first reaction sequence

The first reaction sequence comprises the steps of

- in an adduction step providing a C02 adduct of a starting compound comprising a -NFI-CFI2- CH2-NH- moiety or a -NH-CH2-CH2-OH moiety, or HO-CH2-CH2-OH,

- in a chain-extension step reacting a hydroxy-functional compound selected from ethanolamines and dihydroxyethane with an ethyleneamine compound, wherein at least part of the total of hydroxy-functional compounds and ethyleneamine compound is provided in the form of a C02 adduct, to form a C02 adduct of a chain-extended ethyleneamine compound,

- in an elimination step converting a C02 adduct of a chain-extended ethyleneamine compound to the corresponding product ethyleneamine compound by removal of the carbonyl group.

Starting materials for the first reaction sequence are a hydroxy-functional compound selected from ethanolamines and dihydroxyethane, and an ethyleneamine compound. The core of the first reaction sequence is that a hydroxy-functional compound reacts with an amine-functional compound with conversion of a primary amine into a secondary amine or a secondary amine into a tertiary amine. For example, a compound exemplified by formula R-OFI may react with a compound exemplified by the formula FI2NR’, to form a compound exemplified by the formula R-NH-R’, with formation of water. For a further example, a compound exemplified by formula R-OH may react with a compound exemplified by the formula RNR’R”, with formation of water.

Hydroxyl-functional compounds are selected from the group of ethanolamines and dihydroxyethane. In the context of the present specification, the group of ethanolamines encompasses 2-hydroxy-ethylamine, also indicated as monoethanolamine or MEA, and hydroxyethylethyleneamines. Preferred hydroxy-functional compounds include monoethanolamine (MEA), aminoethylethanolamine (AEEA), hydroxyethyl-diethylenetriamine (HE-DETA), hydroxyethyltriethylenetetraamine (HE-TETA), and diethanolamine.

The hydroxyl-functional compound is reacted with an ethyleneamine compound. Ethyleneamine compounds comprise at least one -NH2 group. Preferred ethyleneamine compounds include ethylenediamine (EDA), N-methylethylenediamine (MeEDA), diethylenetriamine (DETA), piperazine (PIP), N-aminoethylpiperazine (AEP), triethylene tetramine (TETA), N, N’-diaminoethylpiperazine (DAEP), tetraethylenepentamine (TEPA), and pentaethylenehexamine (PEHA).

Ethyleneamine compounds may also encompass ethanolamines as described above. If an ethanolamine is used as ethyleneamine compound, the first reaction sequence will result in the formation of (chain-extended) hydroxyethylethyleneamines. If it is desired to manufacture ethyleneamines, the ethyleneamine compound to be reacted with the hydroxyl-functional compound should not be an ethanolamine, but selected from ethyleneamines that do not contain a hydroxygroup.

Some structures of ethyleneamines and hydroxy-functional compounds are provided below:

Preferred examples of product polyethyleneamine compounds are triethylene tetramine (TETA), N,N’-diaminoethylpiperazine (DAEP), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), N-[(2-aminoethyl) 2-aminoethyl]piperazine) (PEEDA), and

1 -[2-[[2-[(2-aminoethyl)amino]ethyl]amino]ethyl]piperazine) (PEDETA).

Adduction step The first step in the first reaction sequence of the present invention is an adduction step, in which a C02 adduct is provided of a starting compound comprising a -NH-CH2-CH2-NH- moiety or a -NH-CH2-CH2-OH moiety, or HO-CH2-CH2-OH. The adduction step can be carried out in various manners.

In one embodiment, the adduction step comprises the step of reacting gaseous C02 with a starting compound comprising a -NH-CH2-CH2-NH- moiety or a -NH-CH2-CH2-OH moiety, or HO-CH2-CH2-OH, resulting in the formation of the respective C02 adducts. This step is also indicated herein as the absorption step.

In another embodiment of the adduction step, the C02 adduct is formed by reaction of a starting compound comprising -NH-CH2-CH2-NH- moiety or a -NH-CH2-CH2-OH moiety, or HO-CH2-CH2-OH with a compound not being C02 which can transfer a carbonyl group to the starting compounds, resulting in the formation of C02 adducts thereof. These compounds can be indicated as carbon oxide delivering agents.

Carbon oxide delivering agents other than C02 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 include urea and derivatives thereof; linear and cyclic ethylene ureas, especially cyclic ethylene urea, mono or di-substituted ethylene ureas, alkyl and dialkyl ureas, linear and 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 C02 or an organic compound that is suitable for use as a carbon oxide delivering agent, or urea or 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

In the above drawing CAEEA again stands for the cyclic 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, U1TETA 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, urea, the carbamate derivative of the ethanolamine-functional compound or the urea derivative of the ethyleneamine compound, or a combination of these. Examples include CMEA, EU, UDETA, and UAEEA, which is the C02 adduct of aminoethylethanolamine.

The embodiment of the adduction step in which the C02 adduct is formed by reaction of a starting compound comprising -NH-CH2-CH2-NH- moiety or a -NH-CH2-CH2-OH moiety, or HO-CH2-CH2-OH with a compound not being C02 which can transfer a carbonyl group to the starting compounds, can also be indicated as a C02 transfer step.

In a preferred embodiment of the present invention, the adduction step is an absorption step in which C02 is absorbed in a reaction medium comprising a starting compound comprising a -NH-CH2-CH2-NH- moiety or a -NH-CH2-CH2-OH moiety, or HO-CH2-CH2-OH to form a C02 adduct of said starting compound and the elimination step is a desorption step in which the C02 adduct of the product polyethyleneamine compound is reacted with water to form the corresponding ethyleneamine compound and C02.

Absorption step

In the absorption step carried out in one embodiment of the process according to the invention, C02 is absorbed in a reaction medium comprising a starting compound comprising a -NH- CH2-CH2-NH- moiety or a -NH-CH2-CH2-OH moiety, or HO-CH2-CH2-OH to form a C02 adduct of said starting compound. C02 adducts of these compounds thus include compounds which a -NH-CH2-CH2-NH- moiety is converted to a urea moiety in which two nitrogen atoms are connected via a carbonyl moiety and an ethylene moiety, in accordance with the following formula:

C02 adducts also include cyclic carbamate compounds

C02 adducts also include compounds in which the HO-CH2-CH2-OH is converted to a ethylenecarbonate molecule which the two O-atoms of HO-CH2-CH2-OH are connected through via a carbonyl moiety and an ethylene moiety. In the above, the C02 adducts are presented as adducts formed by reaction within a single molecule. Of course, C02 adducts can also be formed by reaction of reactive groups of different molecules. Within the context of the present specification a C02 adduct moiety is in many embodiments a moiety wherein two nitrogen atoms, or a nitrogen atom and an oxygen atom, or two oxygen atoms, are connected through a -C(O)- moiety. Furthermore C02 adducts can also form with a single amine or alcohol in a terminal single sided group, i.e. they can be adducts linked to only one nitrogen or oxygen atom.

The absorption step is carried out by contacting C02 with a reaction medium comprising a starting compound comprising a -NH-CH2-CH2-NH- moiety or a -NH-CH2-CH2-OH moiety, or HO-CH2-CH2-OH to form a C02 adduct. The contacting step is to be carried out under such conditions that C02 is absorbed and that a C02 adduct is formed.

Reaction conditions include a reaction temperature which generally is at least 120 ^e C. At a temperature below 120 ^e C, the reaction rate generally is too low to allow meaningful conversion within a reasonable time frame. It may be preferred for the reaction temperature to be at least 140 ^e C, in particular at least 150 ^e C, more in particular at least 170 ^e C. The reaction is generally carried out at a temperature of at most 400 ^e C. The temperature may thus be at most 300 ^e C, in particular at most 250 ^e C, or even at most 220 ^e C. Operating at a temperature of 170-220 ^e C is considered preferred.

The pressure during the reaction is determined for the major part by the provision of C02 to the reaction medium, with the total pressure in the system decreasing during the reaction due to the consumption of C02. In general, the total pressure in the system is at most 75 bara. The total pressure generally is at least 2 bara, in particular at least 5 bara, more in particular at least 10 bara.

The amount of C02 provided to the reaction is not critical. The minimum amount is governed by the amount required to convert the starting material amine compound into its corresponding C02 adduct. Therefore, the molar ratio between C02 and -NH-CH2-CH2-NH- moieties, -NH- CH2-CH2-OH moieties, or HO-CH2-CH2-OH generally is at least 0.1 :1 . A ratio of at least 0.2:1 , in particular at least 0.5:1 may be more attractive if more urea adduct is aimed for. A large excess of C02 is not detrimental to the process, but is generally less attractive for economic reasons. Therefore, as a general maximum a value of 500:1 may be mentioned. The amount of C02 dosed will depend on the desired amount of urea adduct in the final product. In one embodiment, the absorption step is carried out by reacting a compound selected from the group of starting ethyleneamine and hydroxy-functional compounds comprising at least one -NH-CH2-CH2-NH- moiety and at least two ethylene moieties in total, with C02 in the presence of an auxiliary compound selected from ethylenediamine (EDA), monoethanolamine (MEA) and mixtures thereof, the molar ratio of auxiliary compound to amine compound being at least 0.02:1 .

For the process of this embodiment it is preferred for the ethyleneamine compound to be selected from diethylenetriamine (DETA), triethylenetetramine (L-TETA), aminoethylethanolamine (AEEA), and hydroxyethyldiethylenetriamine (HE-DETA). It is preferred for the molar ratio of auxiliary compound to amine compound to be at least 0.05:1 , in particular at least 0.1 :1 , and/or at most 10:1 . It is preferred for the reaction to be carried out at a temperature of at least 120 ^e C, preferably at least 140 ^e C, in particular at least 150 ^e C, more in particular at least 170 ^e C, and/or at most 400 ^e C, in particular at most 350 ^e C, more in particular at most 300 ^e C, still more in particular at most 250 ^e C or even at most 220 ^e C, for example at a temperature of 170-250 ^e C or 170-220 ^e C. It is preferred for the molar ratio between C02 and - NH-CH2-CH2-NH- moieties in the amine compound to be at least 0.5:1 and/or at most 500:1 . It is preferred for the reaction time to be at most 10 hours, in particular at most 6 hours, more in particular at most 3 hours and/or at least 5 minutes, in particular between 0.5 and 2 hours.

In one embodiment, the absorption step is carried out via a two-step process wherein

- in an absorption step a liquid medium comprising an ethyleneamine compound having a linear -NH-CH2-CH2-NH- group is contacted with a C02-containing gas stream at a pressure of at most 20 bara, resulting in the formation of a liquid medium into which C02 has been absorbed,

- bringing the liquid medium to C02 adduct formation conditions, and in a C02 adduct formation step forming a C02 adduct of the ethyleneamine compound, the C02 adduct formation conditions including a temperature of at least 120 ^e C, wherein the total pressure at the end of the C02 adduct formation step is at most 20 bara, wherein the temperature in the absorption step is lower than the temperature in the C02 adduct formation step.

By separating the C02 absorption step from the urea formation step in this embodiment the C02 absorption step can be carried out at relatively low temperatures and pressures. In the absorption step C02 is absorbed in the liquid reaction medium. In the reaction step the absorbed C02 is reacted with the ethyleneamine compound to form an cyclic urea adduct. This means that in the urea formation step the provision of further C02 is not required, and that the absorption step is carried out until sufficient C02 has been absorbed in the liquid medium to achieve the desired conversion of ethyleneamine compound into cyclic ureas in the urea formation step. As indicated above, the provision of further C02 to the reaction medium during the urea formation step (in addition to the C02 provided during the absorption step) is not required, and generally not attractive because it will increase the pressure during the urea formation step. If so desired for some reason, at most 20% of the total C02 required to achieve the desired urea conversion is added during the urea formation step, in particular at most 10%. In one embodiment of this embodiment, the C02-containing gas stream comprises at least 95 vol.% of C02. In another embodiment of this embodiment, the C02-containing gas stream comprises at most 70 vol.% of C02, in particular at most 60 vol.% of C02 and above 0.01 vol.%, in particular between 4 and 60 vol.%. It may be preferred for the step of contacting the liquid medium with the C02-containing gas steam in the absorption step to be carried out at a temperature between 0 ^e C and 200 ^e C, in particular at a temperature of at most 190 ^e C, more in particular at most 150 ^e C, or at most 130 ^e C, more in particular at most 1 10 ^e C and preferably at a value of at least at least 20 ^e C, in particular at least 40 ^e C. It may be preferred for the maximum total pressure in the absorption step to be between 1 and 15 bara, more in particular between 1 and 10 bara, even more in particular between 1 and 3 bara. It may be preferred for the temperature in the urea formation step to be at least 140 ^e C, in particular at least 150 ^e C, more in particular at least 170 ^e C and preferably at most 400 ^e C, in particular at most 300 ^e C, more in particular at most 250 ^e C, or even at most 220 ^e C. The urea formation step is preferably carried out in a closed vessel. It may be preferred for the urea formation step to be carried out in a vessel wherein the volume of the liquid medium in the vessel makes up at least 50% of the total volume of the vessel (including head space), in particular at least 70%, more in particular at least 85%. It may be preferred for the pressure at the end of the cyclic urea formation step is below 15 bara, in particular below 10 bara, in some embodiments below 5 bara, or even below 3 bara.

C02-transfer step

In one embodiment the adduction step comprises a C02 transfer step. In a C02 transfer step, a carbonyl group is provided from a CO source to a starting compound comprising a

-NH-CH2-CH2-NH- moiety or a -NH-CH2-CH2-OH moiety, or HO-CH2-CH2-OH in an adduction step providing a C02 adduct of a starting compound comprising a -NH-CH2-CH2- NH- moiety or a -NH-CH2-CH2-OH moiety, or HO-CH2-CH2-OH. The CO sources have been discussed above. Reaction conditions include a reaction temperature which generally is at least 100 ^e C. At a temperature below 100 ^e C, the reaction rate generally is too low to allow meaningful conversion within a reasonable time frame. It may be preferred for the reaction temperature to be at least 125 ^e C, in particular at least 150 ^e C, more in particular at least 170 ^e C. The reaction is generally carried out at a temperature of at most 400 ^e C. The temperature may thus be at most 300 ^e C, in particular at most 250 ^e C, or even at most 220 ^e C. Operating at a temperature of 170-220 ^e C is considered preferred.

In general, the total pressure in the system is at most 75 bara. The total pressure generally is at least 2 bara, in particular at least 5 bara, more in particular at least 10 bara.

The amount of CO moieties provided to the reaction is not critical. The minimum amount is governed by the amount required to convert the starting material amine compound into its corresponding C02 adduct. Therefore, the molar ratio between CO moieties and independent -NH-CH2-CH2-NH- moieties, -NH-CH2-CH2-OH moieties, or HO-CH2-CH2-OH generally is at least 0.1 :1 . A ratio of at least 0.2:1 , in particular at least 0.5:1 may be more attractive if more urea adduct is aimed for. A large excess of CO moieties is not detrimental to the process, but is generally less attractive for economic reasons. Therefore, as a general maximum a value of 500:1 may be mentioned. The amount of CO moieties dosed will depend on the desired amount of urea adduct in the final product.

Reaction step

In the reaction step of the process according to the invention a hydroxy-functional compound selected from the group of ethanolamines and dihydroxyethane with an ethyleneamine compound, wherein at least part of the total of hydroxy-functional compounds and ethyleneamine compounds is provided in the form of a C02 adduct, to form C02 adduct of a product polyethyleneamine compound.

The reaction step 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. In embodiments where the ethanolamine- functional compound is monoethanolamine the most preferred temperature range is between 230 and 290 °C. The reaction time during the process is in an embodiment between 5 minutes and 15 hours, preferably between 0.5 and 10 hours, more preferably between 1 and 6 hours.

It will be clear to the skilled person that an overly long reaction time will be detrimental, not only for process-economical reasons, but also because it may lead to the formation of undesirable high-boiling side products. A too long reaction time can lead to undesirable degradation and color formation.

If any of the starting compounds contains piperazine units , preferably the reaction is performed in a liquid wherein the liquid comprises water as then both the yield and selectivity can be increased. If one or more of the hydroxy-functional compound, ethyleneamine 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.

As will be clear to the skilled person, the apparatus used in the reaction step, but also in the various other steps of the process according to the invention, should be fit for purpose. That is, they should be able to withstand the long-time interaction with the reactants and products under reaction conditions, including, as described elsewhere, substantial temperatures and pressures. In addition to the reactor and other apparatus being able to withstand the reaction conditions, it is also important that they do no release material which would detrimentally affect the quality of the product produced. For example, as metal ions may result in color formation in the product, the material of construction for the various apparatus should be selected such that metal ions are not released to an unacceptable extent. Suitable materials include, but are not limited to, high quality steels such as austenitic stainless steels, super austenitic stainless steels, ferritic stainless steels, martensitic stainless steels, precipitation-hardening martensitic stainless steels, and Duplex stainless steels. It is within the scope of the skilled person to select suitable materials of construction.

The process can be carried out in one or mutiple 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.

It was found that when adding at least 0.6 molar equivalents of carbon oxide delivering agent on ethyleneamine compound, the yield of ethyleneamines increases considerably and also the amount of side products decreases.

Hence it is preferred to have the molar ratio of C02 and/or carbon oxide delivering agent to ethyleneamine compound at least 0.6 to 1 .

Preferably, the molar amount of C02 and/or carbon oxide delivering agents on ethyleneamine compounds is between 0.7 and 20 molar equivalents of carbon oxide delivering agent on moles of amine functional compound, and more preferably it is between 0.7 and 6:1 , even more preferably between 0.8:1 and 3:1 .

In another embodiment that leads to a high yield, the molar ratio of hydroxy-functional compound to ethyleneamine compound is at least 0.7:1 and the molar ratio of carbon oxide delivering agent to ethyleneamine compound is at least 0.05:1 . In such embodiments the yield of ethyleneamines is also high.

Even more preferably the molar ratio of hydroxy-functional compound to ethyleneamine compound is between 0.8 and 5:1 and the molar ratio of carbon oxide delivering agent to amine functional compound is between 0.2:1 and 20:1 .

Yet even more preferably the molar ratio of hydroxy-functional compound to ethyleneamine compound is between 1 :1 and 2:1 and the molar ratio of carbon oxide delivering agent to ethyleneamine compound is between 0.7:1 and 3:1 .

In one embodiment, to achieve a high selectivity of ethyleneamine on starting materials, especially on hydroxy-functional compound, the molar ratio of hydroxy-functional compound to ethyleneamine compound is preferably between 0.05:1 and 0.7:1 and the molar ratio of C02 and/or carbon oxide delivering agent to ethyleneamine compound is higher than the molar ratio of hydroxy-functional compound to ethyleneamine compound.

More preferably the molar ratio of C02 and/or carbon oxide delivering agent to ethyleneamine compound is at least 10% higher than the molar ratio of hydroxy-functional compound to ethyleneamine compound. In another more preferred embodiment the molar ratio of hydroxy- functional compound to ethyleneamine compound is between 0.1 and 0.5.

It should be noted that carbon oxide delivering agents exist that contain more than one carbonyl group that can be released from the molecule for transfer to the hydroxy-functional compound, such as for example DU-TETA . 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 hydroxyl-functional compound. Accordingly, 1 mole of DU-TETA should be considered 2 moles of carbon oxide delivering agent.

The molar ratio, as above, between compounds is determined by the reactants in the process, independent of the dosing regime used for the reactants.

Elimination step

In the elimination step of the process according to the invention the C02 adduct of polyethyleneamine compound is converted to the corresponding polyethyleneamine compound. It is called an elimination step because the carbonyl group is eliminated from the molecule.

There are various ways to carry out the elimination step.

In one embodiment, the elimination step comprises the step of reacting the C02 adduct of polyethyleneamine compound with water to form C02 and the corresponding ethyleneamine compound. This embodiment is also indicated herein as a desorption step.

In another embodiment the elimination step is carried out by reacting the C02 adduct of polyethyleneamine compound with an inorganic base, resulting in the formation of a polyethyleneamine compound and a carbonate salt. This step is also indicated herein as a caustic treatment step. Within the context of the present invention, an inorganic base is a Lewis or Bronsted base which does not contain carbon-carbon bonds. In many embodiments the inorganic base contains a metal, alkalimetal or alkaline earth metal cation, and in many embodiments it is a Bronsted base. Preferably the inorganic base is a strong inorganic base which is a base that does not contain carbon-carbon bonds and has a pKb of less than 1 .

In another embodiment, the elimination step is carried out by transferring the carbonyl group from the C02 adduct of the polyethyleneamine compound to a compound having a -NH-CH2- CH2-NH- moiety or a NH-CH2-CH2-OH moiety, or HO-CH2-CH2-OH. This step is also indicated as a C02 transfer step.

In one embodiment of the present invention, the elimination step comprises a first elimination step and a further elimination step, wherein the first elimination step and the further elimination step are independently selected from the group of

- a desorption step in which the C02 adduct of polyethyleneamine compound is reacted with water to form C02 and the corresponding polyethyleneamine compound,

- a caustic treatment step in which C02 adduct of polyethyleneamine compound is reacted with an inorganic base, resulting in the formation of a polyethyleneamine compound and a carbonate salt, and

- a C02 transfer step, wherein the carbonyl group from the C02 adduct of the polyethyleneamine compound is transferred to a compound having a -NH-CH2-CH2-NH- moiety or a NH-CH2-CH2-OH moiety, or HO-CH2-CH2-OH,

wherein the first elimination step converts part of the C02 adducts of polyethyleneamines present in the feed thereto into the polyethyleneamine compounds, while part of the C02 adducts of polyethyleneamines present in the feed to the first elimination step is not converted in the first elimination step, and is provided to the second elimination step. Of course, provision of further elimination steps is also possible.

It may be preferred for the first elimination step to be a desorption step or a C02 transfer step and the further elimination step to be a desorption step or a caustic treatment step, wherein the steps are not the same.

In one embodiment the elimination step comprises a desorption step in which not all C02 adducts are converted to polyethyleneamine compounds. Thus, the product resulting from the desorption step may still comprise C02 adducts of polyethyleneamine compounds. If this is the case, it has been found that the C02 adducts are generally C02 adducts of higher polyethyleneamine compounds rather than C02 adducts of lower-boiling starting materials. In this case, if a separation step is carried out, it results in the separation of, in the first place, starting materials, in the second place, a product fraction of higher polyethyleneamine compounds and in the third place a fraction comprising C02 adducts of higher polyethyleneamine compounds.

Desorption step

In the desorption step carried out in one embodiment of the present invention, C02 adducts of ethyleneamine compounds are converted into ethyleneamine compounds by reaction with water, with removal of C02. The reaction takes place in the liquid phase.

The reaction with water generally takes place at a temperature of at least 150 ^e C. If the reaction temperature is below 150 ^e C, C02 adducts of ethyleneamine compounds will not react to a significant extent. It is preferred for the reaction to be carried out at a temperature of at least 180 ^e C, in particular at least 200 ^e C, more in particular at least 230 ^e C, or even at least 250 ^e C. Preferably the temperature during this step does not exceed 400°C, in particular at most 350 ^e C, more in particular at most 320 ^e C.

The pressure during the process is not critical, as long as the reaction medium is in the liquid phase. As a general range, a value of 0.5 to 100 bara may be mentioned, depending on the desired temperature. It is preferred for the C02 removal step to be carried out at a pressure of at least 5 bar, in particular at least 10 bar, to maintain a sufficient amount of amine and water in the medium. In view of the high costs associated with high-pressure apparatus, it may be preferred for the pressure to be at most 50 bar, in particular at most 40 bar.

The amount of water depends on the desired degree of conversion and on the process conditions. In general, the amount of water is at least 0.1 mole water per mole C02 adduct moiety in the feedstock. Higher amounts are often used, e.g., at least 0.2 mole per mole C02 adduct moiety, in particular at least 0.5 mole water per mole C02 adduct moiety. The maximum is not critical for the process according to the invention but too large amounts of water will lead to unnecessarily large equipment being required. As a general maximum an amount of at most 500 mole water per mole cyclic ethylene C02 adduct moiety may be mentioned, in particular at most 300 mole, more in particular at most 200 mole, in some embodiments at most 100 mole, or at most 50 mole.

Depending on the reaction temperature and the desired degree of conversion, the reaction time can vary within wide ranges, e.g., at least one minute, in particular at least 5 minutes, more in particular between 15 minutes and 24 hours. In one embodiment, the reaction time may be at least 30 minutes, or at least 1 hour. It may be preferred for the reaction time to vary between 1 hour and 12 hours, in particular between 1 hour and 6 hours. When using lower temperatures, longer reaction times may be required to obtain the desired degree of conversion. In one embodiment of the present invention, the desorption step is carried out by reacting C02 adducts of ethyleneamine compounds in the liquid phase with water in an amount of 0.1 -20 mole water per mole C02 adduct moiety, at a temperature of at least 230 ^e C, with removal of C02. It has been found that the use of a low amount of water in combination with a relatively high temperature and C02 removal results in an efficient process which good conversion and low formation of side products. It has been found that it is possible in this embodiment of the process according to the invention to obtain good conversion with the relatively limited amount of water of at most 20 mole water per mole C02 adduct moiety. It has been found that it possible to work at even lower amounts of water, e.g., and amount of at most 15 mole water per mole C02 adduct moiety, more in particular an amount of at most 10 mole water per mole C02 adduct moiety, or even at most 5 mole water per mole C02 adduct moiety.

The range of 0.1 -20 mole water per mole C02 adduct moiety refers to the entire amount of water added during the process, calculated on the amount of urea moieties in feedstock at the start of the reaction. To obtain full conversion, 1 mole of water is required per mole C02 adduct moiety to be converted. As full conversion is not always necessary, lower amounts of water may be possible. Therefore, water is used in an amount of at least 0.1 mole per mole C02 adduct moiety. Higher amounts are often used, e.g., at least 0.2 mole per mole C02 adduct moiety, in particular at least 0.5 mole water per mole C02 adduct moiety.

Water can be added at the beginning of the desorption step in a single dosing. It is preferred, however, to add the water during the process, in several dosings or continuously. In a continuous operation multiple feedpoints may be used. By matching the amount of water added to the amount of water consumed by the reaction, the excess water in the reaction mixture can be limited. It has been found that this limits the formation of side products.

The molar ratio of water to urea moieties is calculated on the water present in the liquid reaction medium. If water is added in the form of steam, which may be an attractive embodiment to combine water addition with the provision of heat to the reaction mixture, the majority of water in the steam will not be absorbed in the liquid reaction medium. It is within the scope of the skilled person to regulate the conditions of a water addition process via stream in such a way that the desired amount of water is absorbed by the reaction medium. The water can also be present in the feedstock from the beginning of the reaction, e.g., as a result of the process by which the feedstock was produced. Water can also be added as a liquid. In one embodiment of the desorption step, C02 is removed. C02 removal can be carried out when the conversion of the ethyleneureas into ethyleneamine compounds has been completed. However, it is preferred to carry out C02 removal during the reaction. C02 removal can be carried out in manners known in the art. The most basic way to do this it to vent the reaction vessel. A stripping fluid, in particular a stripping gas can be used to increase C02 removal rate. Other measures to improve removal of C02 will be evident to the skilled person, and include measures like stirring of the reaction mixture, sparging of stripping gas, thin-film evaporation, use of packing or trays, etc.

Where a stripping gas is used, the flow rate is typically at least 1 m3 per 1 m3 reactor volume per hour (at reaction temperature and pressure), and at most 100 m3 per 1 m3 reactor volume per hour (at reaction temperature and pressure). The stripping flow rate can be generated by evaporation of a liquid inside the reactor vessel, resulting in in situ generation of stripping gas. The ranges above also apply to this embodiment. Of course, it is also possible to combine the addition of stripping gas with the in situ formation of stripping gas.

The C02-containing stripping fluid removed from the C02 removal step can, for example, comprise from 1 to 99 mol.% C02. In other embodiments, the stripping fluid may comprise 1 - 80 mol.% C02, or 1 -60 mol.% C02. In some embodiments, the effluent from the C02 removal step may comprise 1 -40 mol.% C02, or 1 -20 mol.% C02. Lower C02 contents make for more efficient stripping, but also for the use of more stripping gas. It is within the scope of the skilled person to find an appropriate balance between these parameters.

If so desired the desorption step can be carried out with water in the presence of an amine compound selected from the group of primary amines, cyclic secondary amines, and bicyclic tertiary amines.

Primary amines are amine functional compounds in which the amine group is of the formula R4-NH ₂ and wherein R4 can be any organic group, preferably an aliphatic hydrocarbon with optional heteroatoms such as oxygen and/or nitrogen. Secondary cyclic amines are amines of the formula R5-NH-R6, wherein R5 and R6 together form a hydrocarbon ring, optionally with heteroatoms such as oxygen and/or nitrogen, preferably a piperazine ring. Tertiary bicyclic amines are amines of the formula R7-N(-R9)-R8 where R7 and R8 together form a hydrocarbon ring - optionally with heteroatoms such as oxygen and/or nitrogen - and R7 and R9 together form another hydrocarbon ring - optionally with heteroatoms such as oxygen and/or nitrogen. On all the above groups R4 to R9 substituents can be present, like alkyl or hydroxyalkyl groups. Primary amines, cyclic secondary amine and bicyclic tertiary amines all contain a sterically relatively unhindered amine group. In this document a compound is defined as a primary amine or a secondary cyclic amine or a tertiary bicyclic amine if one of the amine groups in the compound is a primary amine or secondary cyclic amine or a tertiary bicyclic amine group, independent of if this compound contains further amine groups that may be different in their nature. A compound can also contain two or more different amine functionalities, e.g. a primary amine and a secondary cyclic amine functionality or a primary amine, a secondary cyclic amine and a tertiary bicyclic amine functionality.

Preferred examples of primary amines are alkylamines, linear ethyleneamines, and alkanolamines. Preferred examples of cyclic secondary amines are amines that contain a terminal piperazine ring. Preferred examples of bicylic tertiary amines are 1 ,4- diazabicyclo[2.2.2]octane (DABCO), 1 ,4-diazabicyclo[2.2.2]octan-2-yl)methanol and 1 - azabicyclo[2.2.2]octane (Quinuclidine).

The amine compound is preferably a compound with more than one amine group wherein at least one of the amine groups is a primary amine, even more preferably it is an amine wherein two amine groups are a primary amine.

Preferred amine compounds include ethylenediamine (EDA), N-methylethylenediamine (MeEDA), diethylenetriamine (DETA), ethanolamine (MEA), aminoethylethanolamine (AEEA), piperazine (PIP), N-aminoethylpiperazine (AEP), 1 ,4-diazabicyclo[2.2.2]octane (DABCO), 1 ,4- diazabicyclo[2.2.2]octan-2-yl)methanol, triethylenetetramine (TETA), N-diethyldiamine-2- imidazolidinone (U1TETA), N, N’-diaminoethylpiperazine (DAEP), N, N’-diaminoethyl-2- imidazolidinone (U2TETA), tetraethylenepentamine (TEPA), pentaethylenehexamine (PEHA), and the mono cyclic ureas of TEPA and PEHA (i.e. U1 TEPA, U2TEPA, U1 PEHA, U2PEHA, U3PEHA) and the dicyclic urea isomers of PEHA (i.e. DUPEHA), a polyethyleneimine (PEI) or an ethyleneamine on a solid carrier.

The amine compound is preferably present in a molar amount of between 0.001 and 100 equivalents per mole C02 adduct moiety, more preferably between 0.01 and 50 equivalents, even more preferably between 0.05 and 30 equivalents, yet more preferably between 0.15 and 25 equivalent and most preferably between 0.20 and 20 equivalents.

In the desorption step, C02 adducts of ethyleneamine compounds are converted to C02 and ethyleneamine compounds. It is preferred for at least 10 mole% of the C02 adduct moieties in the system to be converted to the corresponding ethyleneamine moieties. The maximum will depend on the following desorption and recycle steps.

Treatment with (strong) inorganic base In one embodiment, an elimination step is carried out using a (strong) inorganic base. Within the context of the present invention, a strong inorganic base is a base with a material which does not contain carbon-carbon bonds and which has a pKb of less than 1 .

In one embodiment, the strong inorganic base is selected from the group of metal hydroxides, in particular from the group of hydroxides of alkaline and earth alkaline metals, in particular from sodium hydroxide, potassium hydroxide, lithium hydroxide, calcium hydroxide, magnesium hydroxide, and barium hydroxide. In one embodiment, the strong inorganic base is selected from the group of metal oxides, in particular from the group of oxides of alkaline and earth alkaline metals, in particular from calcium oxide, magnesium oxide, and barium oxide. Selecting a strong inorganic base from the group of sodium hydroxide, potassium hydroxide, magnesium (hydr)oxide, and calcium (hydr)oxide may be preferred. The use of sodium hydroxide and potassium hydroxide may be particularly considered preferred. Other strong inorganic bases may also be used, such as ammonium hydroxide. As will be evident to the skilled person, mixtures of various inorganic bases can be used. Compounds comprising a base in addition to other components can also be used, as can be compounds which will be converted into inorganic bases in the reaction medium.

The lower limit of the molar ratio of inorganic base to C02 adduct moieties is not critical. A value of at least 0.2:1 may be mentioned. If it is desired to obtain full conversion of the C02 adduct moieties into the corresponding ethyleneamine compound, the use of larger amounts may be preferred, e.g., in a molar ratio of at least 0.5:1 , in particular at least 1 :1 . It may be preferred to use larger amounts to increase the reaction rate, e.g., a molar ratio of inorganic base to C02 adduct moiety of at least 1 .5:1 , in particular at least 2:1 .

As large amounts of base do not contribute to further conversion but will lead to additional costs, it is preferred for the molar ratio of the inorganic base to the molar amount of C02 adduct moieties in the product provided to the treatment with the inorganic base to be at most 20:1 , in particular at most 15:1 , more in particular at most 10:1 . It has been found that even lower amounts of inorganic base can suffice, in contrast to what has been disclosed in the prior art. More in particular, it has been found that good results can be obtained at a molar ratio of inorganic base to C02 adduct moieties of at most 7.5:1 , in particular at most 6.5:1 , even more in particular at most 5.5:1 . It has been found that the use of a molar ratio of at most 5.5:1 results in full conversion of the C02 adduct moieties and high yield of the resulting ethyleneamine compounds. It may be preferred to use even less inorganic base per mole of C02 adduct moiety, e.g., in a more ratio of at most 5:1 , in particular at most 4:1 , more in particular at most 3:1 . The molar ratio is calculated on the molar amount of C02 adduct moieties in the feed provided to the caustic treatment step. The treatment with inorganic base can, for example, be carried out by contacting the material to be treated with a concentrated aqueous solution of the inorganic base. Depending on the nature of the base and the further composition of the reaction mixture, it may also be possible to add the base in solid form and dissolve it in the reaction medium. As will be clear to the skilled person, the aim is to bring the base in a dissolved state, so that the hydroxy groups can react with the C02 adduct, while avoiding unnecessary dilution of the reaction medium.

The reaction can be carried out at a temperature between room temperature and 400 ^e C. The temperature and pressure should be selected such that the reaction mixture is in the liquid phase. Higher temperatures are advantageous because they lead to decreased reaction times. It may be preferred to carry out the reaction at a temperature of at least 100 ^e C, in particular at least 140 ^e C, in particular at least 170 ^e C. On the other hand, higher temperatures may lead to the undesired formation of side products. It may therefore be preferred to carry out the reaction at a temperature of at most 350 ^e C, in particular at most 280 ^e C.

Depending on the reaction temperature, the reaction time can vary within wide ranges, e.g., between 15 minutes and 24 hours. It may be preferred for the reaction time to vary between 1 hour and 12 hours, in particular between 1 hour and 6 hours. When using lower amounts of base, longer reaction times may be required to obtain the desired degree of conversion.

In one embodiment, as discussed elsewhere herein, the caustic treatment step from the second reaction sequence may be combined with a caustic treatment elimination step from the first reaction sequence. In that case, as the conversion of the C02 adduct of the ethyleneamine compound into the corresponding ethyleneamine compound, requires more stringent conditions than the conversion of the ethyleneamine hydrohalide salt into ethyleneamine. Therefore, if the two reactions are to be combined in a single step, the conditions and the amount of base should be selected such that both reactions take place. The conditions described above for the conversion of the C02 adduct of the ethyleneamine into the corresponding ethyleneamine should suffice.

Upon completion of the reaction, a reaction mixture will be obtained which contains ethyleneamine compounds and a carbonate salt of the inorganic base. The salt can be removed by methods known in the art, e.g., by filtration where the salt is in solid form.

The process according to the invention can be carried out in batch operation, fed-batch operation, or in a continuous operation, e.g., in a cascade of continuous flow reactor. Depending on the scale of the operation, continuous operation may be preferred.

Combination of elimination steps A particular combination of elimination steps include a desorption step followed by a treatment with strong inorganic base, optionally after a separation step in which desired compounds have been removed..

In one embodiment, this combination encompasses the conversion of cyclic ethyleneureas into their corresponding ethyleneamines by a process comprising

- in a first step converting cyclic ethyleneureas into their corresponding ethyleneamines by reacting cyclic ethyleneureas in the liquid phase with water with removal of C02, so as to convert between 5 mole% and 95 mole% of ethyleneurea moieties in the feedstock to the corresponding amines, and

- in a second step adding a inorganic base and reacting cyclic ethylene ureas remaining from the first step with the inorganic base to convert them completely or partially into their corresponding ethyleneamines.

Another particular combination of elimination steps include a combination of one or more desorption steps with one or more reactive separation steps. The reactive separation encompasses C02 transfer wherein the carbonyl group from the C02 adduct of the product polyethyleneamine compound is transferred to a compound having a -NH-CH2-CH2-NH- moiety or a NH-CH2-CH2-OH moiety, or HO-CH2-CH2-OH.

In one embodiment this combination encompasses the conversion of a feedstock comprising cyclic ethyleneureas into their corresponding ethyleneamines, by a process comprising

- a desorption step in which cyclic ethyleneureas are converted into their corresponding ethyleneamines by reacting cyclic ethyleneureas in the liquid phase with water with removal of C02,

- a reactive separation step wherein cyclic ethyleneureas are converted into their corresponding ethyleneamines by reaction with an amine compound selected from the group of primary amines or secondary amines which have a higher boiling point than the ethyleneamines formed during the process.

The reactive separation step may preferably be carried out as a reactive distillation step. This embodiment is also discussed above in the context of the reaction step.

In one embodiment the desorption step precedes the reactive separation step. In another embodiment, the reactive separation step precedes the desorption step. It is also possible to perform at least two desorption steps, with one or more reactive separation step being performed in between, or at least two reactive separation steps, with one or more reactive desoption steps being performed inbetween.

The reactive separation step may be conducted at any suitable pressure. During the reaction, the pressure in the reactive separation system preferably is at most 127 bara, more preferably at most 50 bara, and even more preferably at most 25 bara. Depending on the composition of the reaction medium, lower pressures may be applied, e.g., less than 15 bar, or less than 5 bar. The process can also be carried out at a pressure below atmospheric pressure, such as less than 700 mbara, more preferably below 100 mbara, even more preferably below 25 mbara, and most preferably below 5 mbara. In general the pressure will be at least 0.1 mbara.

The reactive separation step is preferably carried out at a temperature of at least 150 °C, in particular at least 180 ^e C, in some embodiments at least 200°C, or at least 230°C, sometimes at least 250°C. Preferably the temperature during the process does not exceed 400°C, more preferably 350 °C. In one embodiment, the reactive separation step amine removal step is carried out at a temperature in the range of 180-300 ^e C and a pressure of at most 2000 mbara, in particular at most 1000 mbara, more in particular at most 500 mbara, more in particular at most 200 mbara. It may be preferred to carry out the reactive separation step at a temperature of 200-260 ^e C and a pressure of at most 50mbara. The reactive separation step generally is performed for a time of between 1 minute and 12 hours. Preferably the reactive separation step is run in less than 10 hours, more preferably in less than 8 hours, most preferably less than 5 hours.

In some embodiments it is favorable to at least partially combine the reaction step with the separation, and/or elimination step by performing a reactive separation step, such as a reactive distillation. In a reactive separation step the above reaction step finds place under conditions selected such that the C02 adduct of the starting compounds reacts to give C02 adduct of product polyethyleneamine and in the same reactive separation the formed C02 adduct of product polyethyleneamine is either separated from other components, or transfers it CO moiety to another component in the reactor, which can be either remaining starting compounds or byproducts.

In one embodiment C02 adducts of ethyleneamine compounds are converted into their corresponding ethyleneamine compounds by reaction with an amine compound chosen from the group of primary amines or secondary amines that have a higher boiling point than the ethyleneamine compounds formed during the process, wherein the process is a reactive separation process and the reaction mixture contains less than 10 wt% of water on the basis of total weight of the reaction mixture. It may be preferred to carry out the reaction in less than 7 wt% of water on total reaction mixture. It may be preferred for the pressure to be less than 25 bara, in particular less than 500 mbara. In general, the reaction will be done at a temperature of at least 150°C. The second reaction sequence

The second reaction sequence comprises the steps of

- in an amination step reacting monoethanolamine with ammonia in the presence of hydrogen and an amination catalyst to form a reaction mixture comprising ethylenediamine,

- in a separation step separating the reaction mixture derived from the amination step into at least two fractions.

In the process of the present invention at least one amination step takes place.

The reaction of a compound comprising a hydroxyl-group with a compound selected from ammonia and compounds comprising an amine group may be indicated as a reductive amination reaction. The transfer of an amino group from one molecule to another, or within the same molecule may be indicated as a transamination reaction. As will be evident to the skilled person, in a reactor containing a compound comprising a hydroxyl-group, e.g., monoethanolamine, and compounds comprising amino groups both reductive amination reactions and transamination reactions will take place. Therefore, in the present specification the term amination step will be used. The term transamination will only be used for the specific situation that compounds comprising a hydroxyl-group are not present in the system.

The second reaction sequence comprises an amination step in which monoethanolamine is reacted with ammonia in the presence of hydrogen in the presence of an amination catalyst to form a reaction mixture comprising ethylenediamine.

The reaction mixture provided to the reaction may comprise further components, such as hydroxyl-functional compounds such as aminoethylethanolamine (AEEA), hydroxyethyl- diethylenetriamine (HE-DEATA), diethanolamine (DEA), and hydroxyethyl- triethylenetetramine (HE-TETA), and ethyleamine compounds such as N- methylethylenediamine (MeEDA), diethylenetriamine (DETA), piperazine (PIP), N- aminoethylpiperazine (AEP), triethylene tetramine (TETA), N, N’-diaminoethylpiperazine (DAEP), tetraethylenepentamine (TEPA), and pentaethylenehexamine (PEHA). These compounds can be provided from external sources, but also as recycle streams from other steps from the second and first reaction sequences.

The second reaction sequence can also comprise one or more further amination steps. In one embodiment, the second reaction sequence comprises at least one further amination step wherein an ethyleneamine reactant is reacted with compound selected from ammonia or a further ethyleneamine reactant in the presence of hydrogen and an amination catalyst. In this embodiment, the ethyleneamine reactant may be selected from the group of hydroxyl- functional compounds and amine-functional compounds as stated above. Specific embodiments of further amination steps comprise:

- an amination step wherein EDA is reacted to form higher ethyleneamines

- an amination step wherein EDA is reacted with MEA to form higher ethyleneamines

As will be evident to the skilled person, in all cited steps further compounds may also be present, and appropriate recycles may be applied.

In one embodiment, the process according to the invention encompasses at least two amination steps wherein in the first amination step monoethanolamine is reacted with ammonia, to form ethylenediamine and further compounds, and in a second amination step ethylenediamine is reacted in the presence of hydrogen and a catalyst to form higher ethyleneamines, wherein higher ethyleneamines are defined as ethyleneamines which contain more ethylene moieties than ethylenediamine. Of course, some higher ethyleneamines will also be formed in the first amination step.

In one embodiment, EDA from the first amination step is provided as starting material to the second amination step. The product from the second amination step can be provided to the separation step. While it is possible to provide the entire effluent from the first amination step to the second step, it may be preferred to carry out an intermediate separation step, and provide in particular EDA to the second amination step. It is possible to provide MEA to the second amination step, but this is an optional embodiment.

Where the amination reaction encompasses the reaction of an ethanolamine such as monoethanolamine or aminoethylethylethanolamine with ammonia, the reaction is generally carried out at a temperature in the range of 120-225 ^e C. Ammonia is generally added in an excess amount of at least 3 moles per mole ethanolamine, in particular at least 5 moles per mole ethanolamine, more in particular at least 10 moles per mole ethanolamine. Pressure is generally in the range of 5-30 MPa, in particular 10-20 MPa.

Where ammonia is not present in the amination reaction, the reaction is generally carried out at a temperature in the range of 130-200 ^e C, in particular in the range of 140-180 ^e C. The pressure is generally in the range of 5 to 40 MPa, more in particular in the range of 10 to 20 MPa.

Catalysts suitable for use in amination are known in the art. Suitable catalysts include catalysts comprising at least one metal component on a porous inorganic carrier. Examples of metal components are nickel, rhenium, cobalt, iron, copper, platinum and palladium. The use of nickel-based catalysts is known to be attractive in amination processes. It is within the scope of the skilled person to select a suitable amination catalyst and process conditions.

Conversion of ethyleneoxide and ammonia to monoethanolamine

In one embodiment of the present invention, a step of manufacturing monoethanolamine from ethyleneoxide and ammonia is present in the process according to the invention. This ethyleneoxide conversion step can be present in the second reaction sequence to manufacture the monoethanolamine provided to the amination step. It can also be present in the first reaction sequence to provide monoethanolamine to the adduction step or the chain extension step. In a preferred embodiment of the invention, monoethanolamine derived from the ethyleneoxide conversion step is provided to both the first reaction sequence and the second reaction sequence, as this makes it possible to use the widely available starting materials ethyleneoxide and ammonia to manufacture a wide variety of products.

The reaction of ethyleneoxide and ammonia may generate dihydroxyethyleneamine (DEA) as side product. In one embodiment of the present invention, DEA generated in the ethyleneoxide conversion step is provided to the adduction step or the chain extension step of the first reaction sequence, where it can serve as a starting material for reaction with an ethyleneamine compound, to manufacture higher ethyleneamines.

The reaction of ethyleneoxide and ammonia to form monoethanolamine is known in the art. In general, ethyleneoxide and ammonia are reacted in the condensed phase at a temperature of 20-250 ^e C, with a pressure sufficient to keep the components in the condensed phase. Ammonia will generally be provided in an excess, with the molar ratio of ammonia to ethyleneoxide being, e.g., in the range of 10:1 to 80:1 . Ammonia may be provided in anhydrous form, or in an aqueous solution. In one embodiment, especially where ammonia is provided in anhydrous form, an acid catalyst, in particular a solid acid catalyst may be present. As processes for manufacturing monoethanolamine from ethyleneoxide and ammonia are known in the art, it requires no further elucidation here.

Connection of the first and second reaction sequences

In the process according to the invention, the first reaction sequence and the second reaction sequence are connected in that at least one of the following takes place: - effluent from a step in the first reaction sequence is provided as starting material to a step in the second reaction sequence,

- effluent from a step in the second reaction sequence is provided as starting material to a step in the first reaction sequence,

- a step from the first reaction sequence and a step from the second reaction sequence are combined, or

- effluent from a step in the first reaction sequence is combined with effluent from a step in the second reaction sequence.

There are numerous ways in which the first reaction sequence and the second reaction sequence can be connected.

In one embodiment of the present invention product from the amination step in the second reaction sequence is provided to the adduction step or the reaction step in the first reaction sequence, directly, or with an intermediate separation step being carried out.

This embodiment is considered advantageous because it allows the use of low-molecular weight ethyleneamine compound fractions generated in the second reaction sequence, e.g., AEEA, PIP, DETA, and EDA, to be used as starting material in the manufacture of higher molecular weight ethyleneamine compounds through the process of the first reaction sequence.

This embodiment may be particularly advantageous where EDA, DETA, and/or AEEA produced in amination step is provided to the adduction step or chain extension reaction step. In the case of EDA the process can be carried out with MEA and ammonia as starting materials for the second reaction sequence and MEA and EDA, the latter derived from the second reaction sequence, as starting materials for the first reaction sequence. This makes it possible to prepare a wide variety products from widely available and inexpensive starting materials. This embodiment combines the advantages of the two reaction sequences, in that the first reaction sequence makes it possible to obtain higher ethyleneamine products, but is less effective in doing so starting from ammonia, while the second reaction sequence can use the combination of MEA and ammonia as starting material, but has been found to be less selective when the aim is to manufacture higher ethyleneamine products.

Additionally, connecting the two reaction sequences in this manner makes it possible to obtain increased product slate flexibility by allowing shifting the output from products which are less in demand to products which are more in demand. One way of performing this embodiment is illustrated in Figure 1 and Figure 2A. A variation on this embodiment is described in Figure 5. In one embodiment of the present invention product from the amination step and product from the elimination step are combined and provided to a separation step. Various ways of combining the separation steps may be envisaged, ranging from combining the entire product of both reaction sequences combining the entirety of the product of one reaction sequence with part of the product of the other reaction sequence, and combining part of the product of one reaction sequence with part of the product from another reaction sequence. In general, combining separation steps makes for increased efficiency from an operating point of view, both as regards apparatus costs and as regards operating costs. One way of performing this embodiment is illustrated in Figure 2. Another way of performing this embodiment is in Figure 3. In general, combining separation steps may be efficient from a cost point of view, while keeping them separate allows the separation being carried out under optimized conditions, which may allow process efficiency.

In one embodiment product from the chain elongation step of the first reaction sequence is provided to one or more of the amination reaction step and the separation step of the second reaction sequence. This is advantageous because it allows increased process flexibility, which is attractive for reasons given above. One way of carrying out this embodiment is illustrated in Figure 2B (lines 405, 406, respectively).

In one embodiment the product from the elimination step or, where present, separating step from the first reaction sequence is provided to the amination reaction. Again, this is advantageous because it allows increased process flexibility, which is attractive for reasons given above. One way of carrying out this embodiment is illustrated in Figure 2B (lines 407, 408, respectively).

In one embodiment of the present invention the elimination step in the first reaction sequence encompasses a distillation step, and product from the amination step is provided to the distillation step in the elimination step. This embodiments allows the combination of various separation steps into a single unit. This make for more efficient operation and reduction of CAPEX and OPEX.

In one embodiment of the present invention, the second reaction sequence comprises at least one further amination step wherein an ethyleneamine reactant is reacted with compound selected from ammonia or a further ethyleneamine reactant in the presence of hydrogen and an amination catalyst. In particular the further amination step encompasses a step selected from an amination step wherein EDA is reacted to form higher ethyleneamines and an amination step wherein EDA is reacted with MEA to form higher ethyleneamines. A preferred embodiment of the process according to the invention is one in the second reaction sequence encompasses at least two amination steps wherein in the first amination step monoethanolamine is reacted with ammonia, to form ethylenediamine, and in a second amination step ethylenediamine is reacted in the presence of hydrogen and an amination catalyst to form higher ethyleneamines, wherein higher ethyleneamines are defined as ethyleneamines which contain more ethylene moieties than ethylenediamine.

In one embodiment of the present invention product from a further amination step in the second reaction sequence and product from the elimination step in the first reaction sequence are combined and provided to a separation step. This embodiments allows the combination of various separation steps into a single unit. This make for more efficient operation and reduction of CAPEX and OPEX.

In one embodiment of the present product from the first reaction sequence and product from the second reaction sequence are provided to a single purification step. Combining these steps makes for a more efficient use of apparatus, with associated reduction of costs.

In one embodiment, the process further comprises an ethyleneoxide conversion step wherein ethyleneoxide and ammonia are reacted to produce monoethanolamine, and the monoethanolamine is provided to one or more of the amination step, the adduction step, or the chain extension reaction step. The use of monoethanolamine derived from the reaction of ethyleneoxide and ammonia makes for the use of inexpensive widely available starting materials and the presently claimed process is a flexible way of making use of this material. In this way it is possible to obtain higher ethyleneamines from ethyleneoxide and ammonia, without the necessity of providing further EDA compounds. In one embodiment, the process of the present invention comprises the step of reacting ethyleneoxide and ammonia to form monoethanolamine, wherein a first part of the monoethanolamine is provided to the amination step in the second reaction sequence where it is reacted with ammonia to form EDA, which EDA is provided at least in part to the adduction step or the chain-extension step of the first reaction sequence, and wherein a second part of the monoethanolamine is provided to the adduction step or the chain-extension step of the first reaction sequence. This embodiment makes it possible to derive all ethyleneamine and ethanolamine starting materials from ammonia and ethyleneoxide, without the addition of ethyleneamine or ethanolamine compounds from other sources being required. The figures of the present application show various manners in which this can be effected. It will be evident to the skilled person that various manners of connecting the sequences can be combined, even if they are provided in different figures.

The invention will be illustrated with reference to the following figures, without being limited thereto or thereby. For all processes and figures present herein the following applies.

- Intermediate separation steps may be present, also if they are not specified or shown.

- Effluents from process steps can be provided to other process steps in part or in their entirety, whether or not after an intermediate separation step has been carried out.

- Appropriate recycle of starting materials or intermediate products may be carried out, also if it is not specified or shown.

- Purge streams and make-up streams may be present, also if they are not specified or shown.

- Reactants may be provided individually or in combination, also if this is not specified or shown.

- The different steps in the Figures do not necessarily refer to different units or reactors.

- Embodiments of the present invention may be combined, unless they are mutually exclusive.

- Elements of the figures can be combined, and as will be evident from the description, not all elements shown are essential to a specific embodiment.

- Sometimes reaction streams are indicated with the shorthand wording ethyleneamine compound. This wording should not be interpreted as limiting on the content of the fraction, which, as will be evident to the skilled person, may contain other compounds also, e.g., if present, ethanolamine compounds, or, if present, CO adducts of ethyleneamine or ethanolamine compounds.

Figure 1 illustrates a first embodiment of the present invention, in which the two reaction sequences are connected in that effluent from a step in the second reaction sequence is provided to a step in the first reaction sequence.

In Figure 1 , a starting compound comprising a -NH-CH2-CH2-NH- moiety or a -NH-CH2-CH2- OH moiety, or HO-CH2-CH2-OH is provided through line 1 to adduction step 2, where a carbon oxide delivering agent, e.g., C02 or another carbon ode delivering agent is added through line

3. Of course, the CO adduct can also be provided in other manners, as described herein, e.g., through CO transfer. The adduct is provided to a chain-extension reaction step 5 through line

4. Additional reactants can be provided to chain-extension reaction step 5 through lines not shown. For example, if the product from the adduction step is an C02 adduct of an ethyleneamine compound, an ethanolamine compound can be provided to chain-extension reaction step 5. The effluent from the chain-extension reaction step 5 is provided to elimination step 7 through line 6. In the C02 elimination step 7, C02 adduct of ethyleneamine compound is converted to the corresponding ethyleneamine compound, which is withdrawn through line 9. The compound comprising the carbonyl group eliminated from the C02 adduct of the product ethyleneamine compound is withdrawn through line 10. While not essential to the present invention, Figure 1 also contains a separation step 14, which is provided after the elimination step 7. The separation step 14 results in the separation of different fractions. For example, starting materials and/or intermediate compounds can be withdrawn through line 16. They can, if so desired be provided to adduction step 2 and/or chain-extension reaction step 5 through lines not shown. Separation step 14 also yields a product fraction of higher ethyleneamine compounds which is withdrawn through line 15. This part of the figure thus illustrates the first reaction sequence.

In the second reaction sequence, monoethanolamine is provided to an amination reaction step 200 through line 201 . Ammonia is provided through line 202, and hydrogen may be provided through line 203. The product mixture from the amination reaction 200 is provided through line 204 to a separation step 205. The separation step yields at least two fractions. In the embodiment illustrated in this figure, a recycle stream 206 recycles ammonia and optionally hydrogen to the amination reactor 200. A product stream comprising ethyleneamines is withdrawn from the process through line 207. The separation step 205 may yield more fractions than the two which are specified here. All fractions may be processed as desired. For example, product fraction 207 may be submitted to further separation or purification steps not shown. The same goes for other fractions. Line 401 provides a fraction comprising ethyleneamine or ethanolamine compounds having a -NFI-CFI2-CFI2-NFI- moiety or a -NFI-CFI2-CFI2-OFI moiety to the adduction step 2. Examples of suitable compounds are in particular monoethanolamine and ethylenediamine, but higher molecular weight compounds may also be provided. Line 402 provides a fraction comprising ethyleneamine or ethanolamine compounds to the chain extension step 6. The composition of the two fractions in lines 401 and 402 may be the same or different, and it will be clear to the skilled person that it is also possible to have only one of fractions 401 and 402. In one embodiment this fraction comprises cyclic compounds such as piperazine or aminoethylpiperazine which, upon further processing in the first reaction sequence can result in the formation of higher ethyleneamine compounds containing piperazine rings, e.g., piperazinoethyl ethylenediamine (PEEDA), diaminoethylpiperazine, and the piperazine-ring-containing penta- and hexaethyleneamines. The embodiment of Figure 1 is considered advantageous because it allows the use of low- molecular weight ethyleneamine compound fractions generated in the second reaction sequence, e.g., AEEA, PIP, DETA, and EDA, to be used as starting material in the manufacture of higher molecular weight ethyleneamine compounds through the process of the first reaction sequence.

This embodiment may be particularly advantageous where EDA produced in amination step 200 is provided to adduction step 2 or chain extension reaction step 5. In that case the process can be carried out with MEA and ammonia as starting materials for the second reaction sequence and MEA and EDA, the latter derived from the second reaction sequence, as starting materials for the first reaction sequence. This makes it possible to prepare a wide variety products from widely available and inexpensive starting materials. A variation on this embodiment is described in Figure 5.

Figure 2 illustrates a second embodiment of the present invention, in which the two reaction sequences are connected in that effluent from a step in the first reaction sequence is provided to a step in the second reaction sequence.

Figure 2 shows the same entities as Figure 1 . However, instead of lines 401 and 402 present in Figure 1 , in Figure 2 a fraction is withdrawn from elimination step 7, through line 403 and provided to separation step 205. A fraction from separation step 404 of the first reaction sequence can be provided to separation step 205 of the second reaction sequence through line 404. it will be clear to the skilled person that it is also possible to have only one of fractions 403 and 404.

This embodiment allows efficient and cost-effective tailoring of the separation steps. Further, this process allows the provision of compounds, in particular low-molecular weight compounds such as MEA, EDA, DETA, AEEA, and PIP, which may be present in the reaction mixture of the reaction formed in the first reaction sequence to be processed in an efficient manner in the second reaction sequence. In Figure 2 these fractions are provided to the separation step 205 through line 404, where they may be part of the recycle fraction provided to the amination step 200 through line 206. . It is also possible to provide a fraction originating from separation step 14 to amination step 200 through lines not shown.

Figure 2A illustrates a preferred embodiment of the present invention, in which all of lines 401 , 402, 403, and 404 are presented. This figure thus is an illustration of a preferred embodiment of the present invention in which with the first reaction sequence and the second reaction sequence are connected in that: - ethyleneamine produced in the second reaction sequence is provided to the absorption step and/or the chain extension step in the first reaction sequence, and

- ethyleneamine product from the salt separation step in the second reaction sequence is provided to a fractionation step, where it is fractionated into different ethyleneamine product fractions, and an ethyleneamine compound fraction is withdrawn from the elimination step in the first reaction sequence and provided to said fractionation step from the second reaction sequence and/or a product withdrawn from a separation step in the first reaction sequence is provided to the fractionation step in the second reaction sequence.

This combination of providing one or more fractions from the fractionation step in the second reaction sequence to the first reaction sequence and vice versa allows a particularly efficient use of equipment, and makes it possible to tailor the nature of the products produced to the market demand. It is possible to have either or both of streams as illustrated by 401 and 402 and either or both of streams as illustrated by 403 and 404.

Figure 2B illustrates a further embodiment of the present invention. In addition to lines 401 , 402, 403, and 404 from Figure 2A, Figure 2B also encompasses the following lines:

405 ethyleneamine compound from chain extension step to step to amination reaction step

406 ethyleneamine compound from chain extension step to step to separation step

407 ethyleneamine compound from elimination step to amination reaction step

408 ethyleneamine compound from separation step of first sequence to amination reaction step

As will be evident to the skilled person, it is not necessary to have all these lines in combination. This is certainly possible, however. It is within the scope of the skilled person to select which streams best match the desired product profile, also taking the available starting materials into account.

Figure 3 illustrates an embodiment of the present invention in which a step of the first reaction sequence and a step of the second reaction sequence are combined. More in particular, effluent from the elimination step 7 and effluent from the amination step 200 are both provided to a separation step 208. In separation step 208, a number of different streams are generated, examples of which are illustrated in Figure 3. A first fraction comprising ammonia and optionally hydrogen is withdrawn through line 209. This fraction can, if so desired, be recycled in whole or in part to amination step 200. A further fraction comprising relatively light components such as monoethanolamine and diethanolamine is withdrawn through line 210. This fraction can be provided in its entirety or in part, to one or more of amination step 200, adduction step 2, or chain extension reaction step 5, depending on the composition of the fraction, the products aimed for, and the starting materials available. A product fraction comprising compounds aimed for, e.g., one or more of diethylenetriamine (DETA), triethylenetetramine (TETA), and tetraethylenepentamine (TEPA) can be withdrawn through line 21 1 . A fraction containing higher boiling compounds, e.g., compounds still comprising a cyclic urea moiety can be withdrawn through line 212. As will be evident to the skilled person, it is possible to have more or fewer streams generated by separation step 208. The four streams discussed here are examples only.

The use of a combined separation section as is illustrated in this embodiment enables more efficient use of separation equipment, and efficient tailoring of product fractions depending on prevailing market conditions.

Figure 4 illustrates a variation on Figure 1 wherein a transamination step 213 has been included. In this embodiment, an effluent stream comprising EDA is withdrawn from separation step 205 through line 214 and provided to transamination step 213, where it is reacted in the presence of a catalyst in contact with hydrogen provided through line 215. As will be evident to the skilled person, hydrogen does not have to be provided through a separate line. It can also be introduced in the step in combination with other streams. The same applies to the provision of hydrogen to amination step 200. Flydrogen streams in the process according to the invention can derive from the same or different sources. Flydrogen can be recycled as desired. Monoethanolamine may be provided through lines not shown. The reaction product comprising higher ethanolamines is provided to separation step 205 through line 216.

In the embodiment illustrated here, the effluent from amination step 200 and transamination step 213 are both coupled separately to separation step 205. As will be evident to the skilled person, it is also possible to carry out, sequentially, an amination step, a separation step, a transamination step, and a further separation step.

As will also be clear to the skilled person it is also possible to provide effluent streams comprising EDA which derive from other sources to the transamination step. Examples include streams comprising EDA derived from the chain extension reaction step, the elimination step, and the separation step.

The process of this embodiment containing two amination steps makes it possible to manufacture an increased amount of higher ethyleneamine compounds in a controlled and efficient manner. Additionally, the presence of two amination steps in the second reaction sequence in combination with the first reaction sequence makes for increased process flexibility, by being able to increase the capacity for manufacturing higher ethyleneamines (which are mainly produced in the chain extension step in the first reaction sequence and in the second amination step in the second reaction sequence) on demand.

Figure 5 shows a further embodiment of the present invention, which also comprises an ethyleneoxide conversion unit 217. In ethyleneoxide conversion unit 217 ethyleneoxide provided through line 218 is reacted with ammonia provided through line 219, to form monoethanolamine. The monoethanolamine can be provided as starting material to the amination step 200 through line 201 . It can also be provided to the adduction step 2 through line 1 , or to the chain extension reaction step 5 through line 220, whichever is desired. The ammonia from line 219 can be derived from the same source as the ammonia provided through line 202, or from a different source. It can also be derived from separation step 205 through a line not shown.

Streams 401 and 402 are not necessary in this embodiment, but their presence is advantageous for the reasons discussed for Figure 1 above. The use of ammonia and ethyleneoxide as illustrated in this figure can advantageously be combined with the recycle of compounds through one or more of lines 401 , 402 403, 404, 405, 406, 407, and 408 as illustrated in Figures 2A and 2B. As will be evident to the skilled person, it is not necessary to have all these lines in combination. This is certainly possible, however. It is within the scope of the skilled person to select which streams best match the desired product profile, also taking the available starting materials into account.

The embodiment of the invention of which figure 5 is an illustration makes it possible to use ammonia and ethyleneoxide as starting materials for a variety of high-value ethyleneamine products.

Reference list

1 starting compound comprising a -NFI-CFI2-CFI2-NFI- moiety or a -NFI-CFI2-CFI2-OFI moiety, or HO-CH2-CH2-OH

2 adduction step

3 carbon oxide delivering agent, e.g.,C02

4 effluent from adduction step

5 chain extension reaction step

6 effluent from chain extension reaction step

7 elimination step

9 ethyleneamine compound

10 compound comprising carbonyl group 14 separation step

15 ethyleneamine compound product fraction

16 starting materials and/or intermediate products

200 amination reaction step

201 provision of monoethanolamine

202 ammonia

203 hydrogen

204 product mixture from amination reaction step

205 separation step

206 recycle stream of ammonia and optionally hydrogen

207 product stream

208 separation step

209 fraction comprising ammonia and optionally hydrogen

210 fraction comprising light components

21 1 product fraction

212 fraction containing higher-boiling components

213 transamination step

214 effluent stream comprising EDA

215 hydrogen

216 product of transamination step

217 ethyleneoxide conversion unit

218 ethyleneoxide

219 ammonia

220 MEA401 ethyleneamine compound to adduction step

402 ethyleneamine compound to chain extension reaction step

403 ethyleneamine compound from elimination step to separation step

404 ethyleneamine compound from separation step of first sequence to separation step of second sequence

405 ethyleneamine compound from chain extension step to step to amination reaction step

406 ethyleneamine compound from chain extension step to step to separation step

407 ethyleneamine compound from elimination step to amination reaction step

408 ethyleneamine compound from separation step of first sequence to amination reaction step