CN113557224A

CN113557224A - Method for producing ethylene amine compound

Info

Publication number: CN113557224A
Application number: CN202080016489.5A
Authority: CN
Inventors: A·J·B·登·凯特; R·K·埃德文森; M·J·T·瑞秋马克斯; R·维尼曼; S·约维察; L·F·祖贝尔; E·N·坎特兹; 伊娜·埃勒斯; H·万·丹; K·F·拉克
Original assignee: Norion Chemicals International Ltd
Current assignee: Norion Chemicals International Ltd; Nouryon Chemicals International BV
Priority date: 2019-02-13
Filing date: 2020-02-13
Publication date: 2021-10-26

Abstract

The present invention discloses a process for the manufacture of an ethylene amine compound selected from the group consisting of ethylene amines and hydroxyethylethylene amines, wherein the process comprises two reaction sequences, the first reaction sequence comprising the steps of: in the addition stepFor containing-NH-CH₂‑CH₂-NH-moiety or-NH-CH₂‑CH₂-OH moiety or HO-CH₂‑CH₂CO of the OH starting compound₂An adduct, -in the step of chain extension, reacting a hydroxy-functional compound selected from ethanolamine and dihydroxyethane with an ethyleneamine compound, wherein at least a portion of the sum of the hydroxy-functional compound and the ethyleneamine compound is reacted with CO₂Provided in the form of an adduct to form CO of the chain extended ethyleneamine compound₂Addition, in an elimination step, CO of the chain-extended ethyleneamine compound is removed by removal of the carbonyl group₂The adduct is converted to the corresponding product ethyleneamine compound and 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 from the amination step into at least two fractions, wherein a first reaction sequence is linked to a second reaction sequence such that at least one of the following occurs: -providing the effluent from the steps in the first reaction sequence as starting material to the steps in the second reaction sequence, -providing the effluent from the steps in the second reaction sequence as starting material to the steps in the first reaction sequence, -combining the steps of the first reaction sequence with the steps of the second reaction sequence, or-combining the effluent from the steps in the first reaction sequence with the effluent from the steps in the second reaction sequence. The process according to the invention combines the flexibility of the starting materials and products used with efficient use of the plant and efficient treatment of waste streams.

Description

Method for producing ethylene amine compound

The present invention relates to the production of an ethylene amine compound selected from ethylene amines and hydroxyethylethylene amines.

Ethylene amine compounds, more specifically ethylene amines and hydroxyethylethylene amines, are useful in many applications. Ethyleneamines consist of two or more nitrogen atoms connected by ethylene units. The ethyleneamines may be straight-chain H₂N(-CH₂-CH₂-NH)_p-H is present in the form. This means Ethylenediamine (EDA), Diethylenetriamine (DETA), linear triethylenetetramine (L-TETA) and Linear Tetraethylenepentamine (LTEPA), respectively. Obviously, this range can be extended. Using three or more ethylene units, branched ethylene amines such as N (CH) may also be produced₂-CH₂-NH₂)₃Triaminoethylamine (TAEA). Two adjacent nitrogen atoms may be linked by two ethylene units to form a piperazine ring. The piperazine ring can be present in a longer chain to produce the corresponding piperazine ring-containing ethyleneamine.

From a commercial standpoint, ethyleneamines, particularly Diethylenetriamine (DETA) and higher ethyleneamines such as linear triethylenetetramine (L-TETA) and Linear Tetraethylenepentamine (LTEPA) are attractive products. In particular, interest in higher ethyleneamines is increasing, because these compounds have numerous commercial applications, for example as starting materials or in: asphalt additives, corrosion inhibitors, epoxy curing agents, fabric softeners, fuel additives, hydrocarbon purification, ion exchange resins, lubricating oil additives, paper wet strength resins, petroleum production chemicals, solvents, synthetic resins such as amide resins, mineral processing aids, and interfacial active materials (surfactants).

Hydroxyethylethylene amine is used in chemical processes as a solvent or as a reactant. For example, of the formula H₂N-CH₂-CH₂-NH-CH₂-CH₂-OH aminoethylethanolamine (AEEA) is an organic base used in the industrial manufacture of fuel and oil additives, chelating agents and surfactants. Chain-extended ethanolamines, e.g. of formula H₂N-(CH₂-CH₂-NH)q-CH₂-CH₂Monoethanolamine compounds of-OH (where q is 2 or greater) are interesting intermediates for various types of organic synthesis, e.g., carboxylic ester manufacture. They can also be used, for example, in the formation of synthetic resins, as surfactants, in the production of emulsifiers, in fabric softeners and as epoxy hardeners.

Nowadays, EDC (dichloroethane) -based processes are the main process for producing higher ethyleneamines, which for the purposes of this specification are defined as ethyleneamines having at least two ethylene moieties. The EDC route is a substitution reaction of EDC (dichloroethane) with ammonia and/or ethylene amines at elevated temperature and pressure to form the hydrochloride salt of ethylene amine, which is then reacted with caustic to form a mixture of ethylene amine and NaCl. The EDC route has its disadvantages. This route relies on the use of dichloroethane which is expensive, difficult to dispose of and associated with Health Safety and Environmental (HSE) issues. In addition, the EDC route produces a mixture of many different ethyleneamines. Nevertheless, it remains an attractive process for the manufacture of ethyleneamines, as evidenced by its widespread use.

In view of the fluctuating market conditions for ethyleneamine compounds and starting materials used in their manufacture, there is a need in the art for a process that provides flexibility in the products produced and starting materials used. There is also a need in the art for a method that combines the flexibility of starting materials and products used with the efficient use of equipment and the efficient treatment of waste streams. The present invention provides a solution to these problems.

The invention relates to a method for producing an ethylene amine compound selected from the group consisting of ethylene amines and hydroxyethylethylene amines, wherein the method comprises two reaction sequences,

the first reaction sequence comprises the following steps

-in the addition step, providing a catalyst comprising-NH-CH₂-CH₂-NH-moiety or-NH-CH₂-CH₂-OH moiety or HO-CH₂-CH₂CO of the OH starting compound₂The addition product of the acid-base-modified acrylic acid,

-reacting, in a chain extension step, a hydroxy-functional compound selected from ethanolamine and dihydroxyethane with an ethyleneamine compound, wherein at least a portion of the sum of the hydroxy-functional compound and the ethyleneamine compound is reacted with CO₂Provided in the form of an adduct to form CO of the chain extended ethyleneamine compound₂The addition product of the acid-base-modified acrylic acid,

-in the elimination step, the CO of the chain-extended ethyleneamine compound is removed by removing the carbonyl groups₂The adduct is converted to the corresponding product ethyleneamine compound, and

the second reaction sequence comprises the following steps

-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, the reaction mixture from (derived from) the amination step is separated into at least two fractions,

wherein the first reaction sequence is linked to the second reaction sequence such that at least one of:

-providing the effluent from the steps in the first reaction sequence as starting material to the steps in the second reaction sequence,

-providing the effluent from the steps in the second reaction sequence as starting material to the steps in the first reaction sequence,

-combining the steps of the first reaction sequence with the steps of the second reaction sequence, or

-combining the effluent from the steps in the first reaction sequence with the effluent from the steps in the second reaction sequence.

The process according to the invention uses two linked reaction sequences to make an ethylene amine compound. Each reaction sequence has its own advantages. The process of the first reaction sequence allows the manufacture of high molecular weight ethylene amine compounds, in particular linear compounds. The process of the second reaction sequence allows for the production of reaction products comprising a mixture of a number of different ethyleneamine compounds in an efficient manner, some of which are interesting as products per se, while others may be more attractive as starting materials for the production of higher ethyleneamine compounds. As will be discussed in more detail below, the process according to the invention allows flexibility in the starting materials used and the products produced, as well as efficient use of the equipment.

One 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, the ethylenediamine formed from monoethanolamine and ammonia in the second reaction sequence is provided to the first reaction sequence where it reacts with monoethanolamine. In this way, a wide variety of products can be obtained from widely available starting materials. In another embodiment, the monoethanolamine provided to one or both reaction sequences is obtained by reacting ethylene oxide with ammonia, allowing the use of even more widely available starting materials.

Another advantage is that ethanolamine compounds such as aminoethylethanolamine, which may be formed as by-products in the second reaction sequence, can be processed via the first reaction sequence, thereby effectively using available equipment.

Another advantage is that specific ethyleneamine compounds containing a piperazine ring, such as piperazinoethylethylenediamine (pema), diaminoethylpiperazine, and piperazine ring-containing pentaethyleneamines and hexaethyleneamines, can be obtained by supplying cyclic compounds, such as piperazine and aminoethylpiperazine, produced in the second reaction to the first reaction sequence.

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

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

Figure 1 shows a first embodiment of the method according to the invention.

Fig. 2, 2a and 2b show further embodiments of the method according to the invention.

Fig. 3 shows a further embodiment of the method according to the invention.

Fig. 4 shows a further embodiment of the method according to the invention.

Fig. 5 shows a further embodiment of the method according to the invention.

Hereinafter, these two separate reaction sequences will be discussed. Next, various ways of linking the reaction sequences will be discussed.

First reaction sequence

The first reaction sequence comprises the following steps

-in the elimination step, the CO of the chain-extended ethyleneamine compound is removed by removing the carbonyl groups₂The adduct is converted to the corresponding product ethyleneamine compound.

The starting materials for the first reaction sequence are a hydroxy-functional compound selected from the group consisting of ethanolamine and dihydroxyethane, and an ethyleneamine compound. At the heart of the first reaction sequence is the reaction of a hydroxyl functional compound with an amine functional compound to convert a primary amine to a secondary amine or a secondary amine to a tertiary amine. For example, a compound of the formula R-OH may be reacted with a compound of the formula H₂NR 'to form a compound of the formula R-NH-R', wherein water is formed. As another example, a compound of the formula R-OH may be reacted with a compound of the formula RNR 'R', wherein water is formed.

The hydroxy-functional compound is selected from the group consisting of ethanolamine and dihydroxyethane. In the context of the present specification, the ethanolamine group includes 2-hydroxy-ethylamine, also denoted as monoethanolamine or MEA, and hydroxyethylethylene amine. Preferred hydroxyl-functional compounds include Monoethanolamine (MEA), aminoethylethanolamine (AEEA), hydroxyethyl-diethylenetriamine (HE-DETA), hydroxyethyl triethylenetetramine (HE-TETA) and diethanolamine.

Reacting a hydroxy-functional compound with an ethyleneamine compound. The ethylene amine compound contains at least one-NH₂A group. Preferred ethyleneamine compounds include Ethylenediamine (EDA), N-methylethylenediamine (MeEDA), Diethylenetriamine (DETA), piperazine (PIP), N-Aminoethylpiperazine (AEP), triethylenetetramine (TETA), N' -Diaminoethylpiperazine (DAEP), Tetraethylenepentamine (TEPA), and Pentaethylenehexamine (PEHA).

The ethyleneamine compounds may also include ethanolamine as described above. If ethanolamine is used as the ethyleneamine compound, the first reaction sequence will result in the formation of (chain-extended) hydroxyethylethyleneamine. If it is desired to make an ethyleneamine, the ethyleneamine compound to be reacted with the hydroxy-functional compound should not be ethanolamine but should be selected from ethyleneamines that do not contain a hydroxy group.

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

preferred examples of the product polyethyleneimine compounds are triethylenetetramine (TETA), N' -diaminoethylpiperazine (dapp), Tetraethylenepentamine (TEPA), Pentaethylenehexamine (PEHA), N- [ (2-aminoethyl) 2-aminoethyl ] piperazine (pema), and 1- [2- [ [2- [ (2-aminoethyl) amino ] ethyl ] Piperazine) (PEDETA).

Addition step

The first step in the first reaction sequence of the present invention is an addition step wherein a catalyst comprising-NH-CH is provided₂-CH₂-NH-moiety or-NH-CH₂-CH₂-OH moiety or HO-CH₂-CH₂CO of the OH starting compound₂An adduct of a carboxylic acid with a carboxylic acid. The addition step can be performed in various ways.

In one embodiment, the addition step comprises passing gaseous CO₂And comprises-NH-CH₂-CH₂-NH-moiety or-NH-CH₂-CH₂-OH moiety or HO-CH₂-CH₂Reaction of the-OH starting compounds leads to the formation of the corresponding CO₂And (3) preparing an adduct. This step is also denoted herein as the absorption step.

In another embodiment of the addition step, CO₂The adduct is prepared by reacting a compound containing-NH-CH₂-CH₂-NH-moiety or-NH-CH₂-CH₂-OH moiety or HO-CH₂-CH₂-OH starting compound with a compound other than CO capable of transferring a carbonyl group to the starting compound₂Thereby leading to the formation of CO thereof₂An adduct is formed. These compounds may be represented as carbon oxide delivery agents.

CO removal within the scope of the invention₂Other carbon oxide delivery agents include organic compounds having carbonyl moieties therein that can be transferred as described above. Organic compounds having a carbonyl moiety include urea and derivatives thereof; linear and cyclic ethylene ureas, especially cyclic ethylene ureas, mono-or disubstituted ethylene ureas, alkyl and dialkyl ureas, linear and cyclic carbamates, organic carbonates and derivatives or precursors thereof. Such derivatives or precursors may include, for example, ionic compounds such asCarbonates or bicarbonates, carbamates and related salts, which, in some embodiments of the methods of the invention, may be converted in situ to their nonionic counterparts, e.g., to linear and cyclic carbamate or urea compounds. When such ionic compounds are used in the present invention, they are carbonates, bicarbonates or carbamates based on organic hydrocarbons. Preferably, the CO delivery agent is CO₂Or an organic compound suitable for use as a carbon oxide delivery agent, or urea or ethylene carbonate, more preferably the carbon oxide delivery agent is added at least in part as carbon dioxide or urea. By using the urea or carbamate compounds described above, the carbon oxide delivery agent may be present in the process in the same molecule as the amine-functional or ethanolamine-functional compound.

Examples of carbon oxide delivery agents include

In the above figure CAEEA then represents the cyclic carbamate of aminoethylethanolamine, UDETA represents the urea of diethylenetriamine, DAEU represents the diaminoethylurea, AE carbamate represents the aminoethylethanol carbamate, CHE-DETA represents the carbamate of hydroxyethyldiethylenetriamine, U1TETA represents the terminal urea of triethylenetetramine and DUTETA represents the 1, 3-diurea of triethylenetetramine.

The carbon oxide delivery agent is most preferably added to the reaction in the form of carbon dioxide, urea, a carbamate derivative of an ethanolamine-functional compound or a urea derivative of an ethyleneamine compound, or a combination of these. Examples include CMEA, EU, UDETA and UEEA, the latter being the CO of aminoethylethanolamine₂An adduct of a carboxylic acid with a carboxylic acid.

Embodiments of the addition step wherein CO₂The adduct is prepared by reacting a compound containing-NH-CH₂-CH₂-NH-moiety or-NH-CH₂-CH₂-OH moiety or HO-CH₂-CH₂The starting compound of-OH with the possibility of transferring the carbonyl group to the starting compound (which may also be denoted as CO)₂Transfer step) of not CO₂Transformation ofA compound is reacted to form.

In a preferred embodiment of the invention, the addition step is an absorption step, wherein CO is added₂Absorbing CO in a reaction medium comprising a starting compound to form said starting compound₂An adduct, the starting compound comprising-NH-CH₂-CH₂-NH-moiety or-NH-CH₂-CH₂-OH moiety or HO-CH₂-CH₂-OH, and the elimination step is a desorption step in which the CO of the product polyethylenamine compound is allowed to form₂The adduct reacts with water to form the corresponding ethyleneamine compound and CO₂。

Absorption step

In the absorption step carried out in one embodiment of the process according to the invention, the CO is fed to the absorption stage₂Absorbing CO in a reaction medium comprising a starting compound to form said starting compound₂An adduct, the starting compound comprising-NH-CH₂-CH₂-NH-moiety or-NH-CH₂-CH₂-OH moiety or HO-CH₂-CH₂-OH. Thus, the CO of these compounds₂The addition product comprises the reaction product of-NH-CH₂-CH₂-the NH-moiety is converted into a compound of a urea moiety according to the following formula, wherein the two nitrogen atoms are connected via a carbonyl moiety and an ethylene moiety:

CO₂the adduct also includes cyclic carbamate compounds;

CO₂the adduct also includes a compound in which HO-CH is added₂-CH₂-OH to ethylene carbonate molecule, wherein HO-CH₂-CH₂These two O atoms of-OH are linked via a carbonyl moiety and an ethylene moiety.

In the above, CO₂The adduct is represented as an adduct formed by a reaction within a single molecule. Of course, CO₂The adduct may also be formed by the reaction of reactive groups of different molecules. In this specificationIn this context, CO is in many embodiments₂An adduct moiety is one in which two nitrogen atoms, or one nitrogen atom and one oxygen atom, or two oxygen atoms, are linked by a-C (O) -moiety. Furthermore, CO can also be formed with a single amine or alcohol in the terminal unilateral group₂The adducts, i.e. they may be adducts attached to only one nitrogen or oxygen atom.

The absorption step is carried out by passing CO₂With a reaction medium comprising a starting compound to form CO₂An adduct, the starting compound comprising-NH-CH₂-CH₂-NH-moiety or-NH-CH₂-CH₂-OH moiety or HO-CH₂-CH₂-OH. The contacting step being the absorption of CO₂And form CO₂Under the conditions of the adduct.

The reaction conditions include a reaction temperature of typically at least 120 ℃. At temperatures below 120 ℃, the reaction rate is generally too low to achieve meaningful conversion in a reasonable time frame. The reaction temperature may preferably be at least 140 ℃, in particular at least 150 ℃, more in particular at least 170 ℃. The reaction is generally carried out at a temperature of at most 400 ℃. The temperature may thus be up to 300 deg.C, in particular up to 250 deg.C or even up to 220 deg.C. It is considered to be preferable to operate at temperatures of 170-220 ℃.

The pressure during the reaction is mainly determined by supplying CO to the reaction medium₂Is determined wherein the total pressure in the system during the reaction is due to CO₂The consumption of (2) is reduced. Typically, the total pressure in the system is at most 75 bar (bara, absolute). The total pressure is generally at least 2 bar, in particular at least 5 bar, more in particular at least 10 bar.

CO supplied to the reaction₂The amount of (a) is not critical. The minimum amount depends on the conversion of the starting material amine compound to its corresponding CO₂The amount of adduct required. Thus, CO₂and-NH-CH₂-CH₂-NH-moiety, -NH-CH₂-CH₂-OH moiety or HO-CH₂-CH₂The molar ratio between-OH groups is generally at least 0.1: 1. If more urea adduct is targeted, then at least 0.2:1, especially up toA ratio as small as 0.5:1 may be more attractive. Large excess of CO₂Is not detrimental to the process but is generally less attractive for economic reasons. Thus, as a general maximum, a value of 500:1 may be mentioned. Dosed CO₂The amount will depend on the amount of urea adduct desired in the final product.

In one embodiment, the absorption step is carried out by subjecting the material selected from the group consisting of at least one-NH-CH₂-CH₂-NH-moieties and a compound of starting ethyleneamines and hydroxy-functional compounds totaling at least two ethylene moieties with CO₂In the presence of an auxiliary compound selected from Ethylenediamine (EDA), Monoethanolamine (MEA) and mixtures thereof, in a molar ratio of auxiliary compound to amine compound of at least 0.02: 1.

For the process of this embodiment, preferably the ethyleneamine compound is selected from the group consisting of Diethylenetriamine (DETA), triethylenetetramine (L-TETA), aminoethylethanolamine (AEEA), and hydroxyethyldiethylenetriamine (HE-DETA). The molar ratio of auxiliary compound to amine compound is preferably at least 0.05:1, in particular at least 0.1:1 and/or at most 10: 1. The reaction is preferably carried out at a temperature of at least 120 ℃, preferably at least 140 ℃, in particular at least 150 ℃, more in particular at least 170 ℃ and/or at most 400 ℃, in particular at most 350 ℃, more in particular at most 300 ℃, still more in particular at most 250 ℃ or even at most 220 ℃, for example 170-. CO in the amine compound is preferred₂and-NH-CH₂-CH₂The molar ratio between the-NH-moieties is at least 0.5:1 and/or at most 500: 1. The reaction time is preferably 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 performed via a two-step process, wherein

-in the absorption step, at a pressure of at most 20 bar, a catalyst comprising a catalyst having a linear-NH-CH₂-CH₂Liquid medium of an ethyleneamine compound having an-NH-group with CO₂Resulting in absorbed CO₂Is formed in the liquid medium of (a),

-allowing a liquid to flowThe medium reaches CO₂Under adduct-forming conditions and in the presence of CO forming an ethyleneamine compound₂CO of the adduct₂In the step of adduct formation, CO₂The adduct forming conditions include a temperature of at least 120 ℃ wherein CO₂The total pressure at the end of the adduct-forming step being at most 20 bar, wherein the temperature in the absorption step is lower than that of CO₂Temperature in the adduct forming step.

In this embodiment, by reacting CO₂The absorption step, separate from the urea formation step, can be carried out at relatively low temperatures and pressures for CO₂And (5) an absorption step. In the absorption step, CO is introduced₂Absorbed in the liquid reaction medium. In the reaction step, the absorbed CO₂With an ethyleneamine compound to form a cyclic urea adduct. This means that no additional CO need be provided in the urea formation step₂And the absorption step is continued until sufficient CO has been absorbed in the liquid medium to effect the desired conversion of the ethyleneamine compound to cyclic urea in the urea formation step₂. As described above, additional CO is provided to the reaction medium during the urea formation step₂(except for the CO provided during the absorption step₂Outside) is not necessary and is generally not attractive as this will increase the pressure during the urea formation step. If this is required for some reason, the total CO required to achieve the desired urea conversion is added during the urea formation step₂At most 20%, in particular at most 10%. In one embodiment of this embodiment, the CO is contained₂Comprises at least 95 vol.% CO₂. In another embodiment of this embodiment, the CO is contained₂Contains at most 70 vol.% CO₂Especially at most 60 vol.% CO₂And higher than 0.01 vol%, in particular between 4 and 60 vol%. It may be preferred to react the liquid medium with the CO-containing gas in the absorption step₂The step of contacting the gas stream of (a) is carried out at a temperature between 0 ℃ and 200 ℃, in particular at a temperature of at most 190 ℃, more in particular at most 150 ℃, or at most 130 ℃, more in particular at most 110 ℃ and preferably at least 20 ℃, in particular at least 40 ℃. In the absorption stepThe maximum total pressure may preferably be between 1 and 15 bar, more particularly between 1 and 10 bar, even more particularly between 1 and 3 bar. The temperature in the urea formation step may preferably be at least 140 ℃, in particular at least 150 ℃, more in particular at least 170 ℃ and preferably at most 400 ℃, in particular at most 300 ℃, more in particular at most 250 ℃ or even at most 220 ℃. The urea formation step is preferably carried out in a closed vessel. The urea formation step may preferably be carried out in a vessel, wherein the volume of liquid medium in the vessel represents at least 50%, particularly at least 70%, more particularly at least 85% of the total volume of the vessel (including the headspace). The pressure at the end of the cyclic urea formation step may preferably be lower than 15 bar, in particular lower than 10 bar, in some embodiments lower than 5 bar or even lower than 3 bar.

CO₂Transfer step

In one embodiment, the addition step comprises CO₂And (5) transferring. In CO₂In the transfer step, the CO source is transferred to the reaction vessel containing-NH-CH in the addition step₂-CH₂-NH-moiety or-NH-CH₂-CH₂-OH moiety or HO-CH₂-CH₂The starting compound of-OH provides a carbonyl group, thereby providing a compound comprising-NH-CH₂-CH₂-NH-moiety or-NH-CH₂-CH₂-OH moiety or HO-CH₂-CH₂CO of the OH starting compound₂An adduct of a carboxylic acid with a carboxylic acid. The source of CO has been discussed above.

The reaction conditions include a reaction temperature of typically at least 100 ℃. At temperatures below 100 ℃, the reaction rate is generally too low to achieve meaningful conversion in a reasonable time frame. The reaction temperature may preferably be at least 125 ℃, in particular at least 150 ℃, more in particular at least 170 ℃. The reaction is generally carried out at a temperature of at most 400 ℃. The temperature may thus be up to 300 deg.C, in particular up to 250 deg.C or even up to 220 deg.C. It is considered to be preferable to operate at temperatures of 170-220 ℃.

Typically, the total pressure in the system is at most 75 bar. The total pressure is generally at least 2 bar, in particular at least 5 bar, more in particular at least 10 bar.

The amount of the CO fraction provided to the reaction is not critical. The minimum amount depends on the conversion of the starting material amine compound to its corresponding CO₂The amount of adduct required. Thus, the CO moiety is separated from the-NH-CH₂-CH₂-NH-moiety, -NH-CH₂-CH₂-OH moiety or HO-CH₂-CH₂The molar ratio between-OH groups is generally at least 0.1: 1. If more urea adduct is targeted, a ratio of at least 0.2:1, in particular at least 0.5:1, may be more attractive. Large excess of CO₂Some are not detrimental to the process but are generally less attractive for economic reasons. Thus, as a general maximum, a value of 500:1 may be mentioned. Dosed CO₂Will depend in part on the amount of urea adduct desired 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 consisting of ethanolamine and dihydroxyethane is reacted with an ethyleneamine compound, wherein at least a portion of the sum of the hydroxy-functional compound and the ethyleneamine compound is reacted with CO₂Provided in the form of an adduct to form CO of the product polyethylene amine compound₂An adduct of a carboxylic acid with a carboxylic acid.

The reaction step is preferably carried out at a temperature of at least 100 ℃. The temperature should preferably be below 400 ℃. More preferably, the temperature is between 200 and 360 ℃. Even more preferably, the temperature is between 230 and 340 ℃. Most preferably, the temperature is between 250 and 310 ℃. In embodiments where the ethanolamine-functional compound is monoethanolamine, the most preferred temperature range is between 230 and 290 ℃.

In one embodiment, the reaction time during the process is 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 too long a reaction time would be detrimental not only for process economics reasons but also because it may lead to the formation of undesirable high-boiling by-products. Excessively long reaction times can lead to undesirable degradation and color formation.

If any of the starting compounds contains piperazine units

It is preferred that the reaction is carried out in a liquid, wherein the liquid comprises water, as this may improve both yield and selectivity. If one or more of the hydroxy-functional compound, the ethylene amine compound or the carbon oxide delivery agent are liquid under the reaction conditions, they are not considered part of the above-described liquid in which the process of the invention is carried out.

In a preferred embodiment, when the compound having piperazine units is present in the process of the invention, the liquid comprises at least 50 wt.% water up to 100 wt.% water, wherein more preferably the remaining up to 50 wt.% is a polar liquid which is homogeneously mixed with water under the conditions used during the process of the invention. Even more preferably, the liquid comprises at least 75 wt.%, still more preferably at least 90 wt.%, most preferably at least 95 wt.% water, based on the total liquid weight.

The reactor employed may be any suitable reactor, including a continuous stirred tank reactor, a pipe reactor, a tubular or multi-tubular reactor. The reactor may be insulated or equipped with external or internal heating means. The feed may be single point or divided into multiple points. It may consist of multiple stages with interstage heat exchange.

It is clear to the person skilled in the art that the equipment used in the reaction steps and in the various other steps of the process according to the invention should be adapted to the purpose. That is, these devices should be able to withstand prolonged interaction with reactants and products under reaction conditions, including, as noted elsewhere, substantial temperatures and pressures. In addition to being able to withstand the reaction conditions, it is also important that reactors and other equipment do not release materials that would adversely affect the quality of the product produced. For example, because metal ions can cause the product to develop color, the materials of construction for various devices should be selected so that metal ions are not released to an unacceptable degree. 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 hardened martensitic stainless steels, and duplex stainless steels. It is within the purview of one skilled in the art to select the appropriate materials of construction.

The process may be carried out in one or more batch reactors, possibly in a fed-batch operation, and/or in a continuous operation system in one reactor or in a cascade of continuous flow reactors, optionally with multiple feed points.

It was found that when at least 0.6 molar equivalents of carbon oxide delivery agent was added to the ethylene amine compound, the yield of ethylene amine was significantly increased and the amount of by-products was also reduced.

Therefore, CO is preferred₂And/or the molar ratio of carbon oxide delivery agent to ethylene amine compound is at least 0.6 to 1.

Preferably, CO on an ethyleneamine compound₂And/or the molar amount of carbon oxide delivery agent is from 0.7 to 20 molar equivalents of carbon oxide delivery agent (based on moles of amine functional compound), more preferably between 0.7 and 6:1, even more preferably between 0.8:1 and 3: 1.

In another embodiment to achieve high yields, the molar ratio of hydroxy-functional compound to ethylene amine compound is at least 0.7:1 and the molar ratio of carbon oxide delivery agent to ethylene amine compound is at least 0.05: 1. In such embodiments, the yield of ethyleneamine is also high.

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

Even more preferably, the molar ratio of hydroxy-functional compound to ethylene amine compound is between 1:1 and 2:1, and the molar ratio of carbon oxide delivery agent to ethylene amine compound is between 0.7:1 and 3: 1.

In one embodiment, to achieve high selectivity of the starting material, especially the ethyleneamine of the hydroxy-functional compound, the molar ratio of hydroxy-functional compound to ethyleneamine compound is preferably between 0.05:1 and 0.7:1 and CO₂And/or the molar ratio of carbon oxide delivery agent to ethylene amine compound is higher than the molar ratio of hydroxy-functional compound to ethylene amine compound.

More preferably, CO₂And/or the molar ratio of carbon oxide delivery agent to ethylene amine compound is at least 10% higher than the molar ratio of hydroxy-functional compound to ethylene amine compound. In another more preferred embodiment, the molar ratio of the hydroxy-functional compound to the ethylene amine compound is between 0.1 and 0.5.

It should be noted that there are carbon oxide delivery agents comprising more than one carbonyl group that can be released from the molecule for transfer to a hydroxy-functional compound, such as DU-TETA. When determining the molar ratio of such compounds, the molar amount of carbon oxide that they can release to transfer to the hydroxy-functional compound should be adjusted. Thus, 1 mole of DU-TETA should be considered as a 2 mole carbon oxide delivery agent.

As mentioned above, the molar ratio between the compounds is determined by the reactants in the process, regardless of the dosing regime used for the reactants.

Eliminating step

In the elimination step of the process according to the invention, the CO of the polyethylene amine compound is reacted₂The adduct is converted to the corresponding polyethylene amine compound. This is called an elimination step, since the carbonyl group is eliminated from the molecule.

There are a number of ways to perform the elimination step.

In one embodiment, the elimination step comprises CO reacting the polyethylene amine compound₂The adduct reacts with water to form CO₂And the corresponding ethylene amine compound. This embodiment is also denoted herein as desorption step.

In another embodiment, the elimination step is carried out by reacting the CO of the polyethylene amine compound₂The adduct reacts with an inorganic base to result in the formation of a polyethylene amine compound and a carbonate. This step is also denoted herein as the alkaline treatment step. In the context of the present invention, an inorganic base is a lewis base or a bronsted base that does not contain carbon-carbon bonds. In many embodiments, the inorganic base is includedContaining a metal, alkali metal or alkaline earth metal cation, and in many embodiments 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 removing the carbonyl group from the CO of the polyethylene amine compound₂Transfer of the adduct to the reaction vessel having-NH-CH₂-CH₂-NH-moiety or-NH-CH₂-CH₂-OH moiety or HO-CH₂-CH₂-OH. This step is also known as CO₂And (5) transferring.

In one embodiment of the invention, the eliminating step comprises a first eliminating step and a further eliminating step, wherein the first eliminating step and the further eliminating step are independently selected from the group consisting of:

-a desorption step, in which the CO of the polyethylene amine compound is allowed to react₂The adduct reacts with water to form CO₂And a corresponding polyethylene amine compound, and a process for producing,

-a base treatment step, in which the CO of the polyethylene amine compound is reacted₂The adduct reacts with an inorganic base resulting in the formation of a polyethylene amine compound and a carbonate, and

-CO₂a transfer step wherein CO from the polyethylene amine compound₂Carbonyl transfer of the adduct to a compound having-NH-CH₂-CH₂-NH-moiety or-NH-CH₂-CH₂-OH moiety or HO-CH₂-CH₂-a compound of the formula-OH,

wherein the first elimination step eliminates CO from the polyethyleneamines present in the feed₂Part of the adduct is converted to a polyethylene amine compound, whereas the CO of the polyethylene amine present in the feed to the first elimination step₂A portion of the adduct is unconverted in the first elimination step and is provided to the second elimination step. Of course, it is also possible to provide additional elimination steps.

It may be preferred that the first elimination step is a desorption step or CO₂The transfer step and the further elimination step are desorption steps or alkaline treatment steps, wherein each step is different.

In one embodiment, the elimination step comprises a desorption step, wherein not all of the CO is present₂The adducts are all converted into polyethylene amine compounds. Thus, the product resulting from the desorption step may still comprise CO of the polyethylene amine compound₂An adduct of a carboxylic acid with a carboxylic acid. If this is the case, CO has been found to be present₂The adduct is usually CO of a higher polyethylene amine compound₂Adducts other than CO of low-boiling starting materials₂An adduct of a carboxylic acid with a carboxylic acid. In this case, if a separation step is carried out, the starting material is firstly separated, the product fraction of the higher polyethylene amine compound is secondly separated, and the CO comprising the higher polyethylene amine compound is thirdly separated₂Fraction of the adduct.

Desorption step

In the desorption step carried out in one embodiment of the present invention, CO of the ethylene amine compound₂The adduct reacts with water and removes CO₂To an ethyleneamine compound. The reaction is carried out in the liquid phase.

The reaction with water is generally carried out at a temperature of at least 150 ℃. If the reaction temperature is less than 150 ℃, CO of the ethylene amine compound₂The adduct will not react to a significant extent. Preferably the reaction is carried out at a temperature of at least 180 ℃, particularly at least 200 ℃, more particularly at least 230 ℃ or even at least 250 ℃. Preferably, the temperature during this step does not exceed 400 ℃, in particular at most 350 ℃, more in particular at most 320 ℃.

The pressure during the process is not critical as long as the reaction medium is in the liquid phase. As a general range, values of 0.5 to 100 bar may be mentioned, depending on the desired temperature. Preference is given to carrying out the CO at a pressure of at least 5 bar, in particular at least 10 bar₂A removal step to maintain sufficient amounts of amine and water in the medium. In view of the high costs associated with high-pressure plants, pressures of up to 50 bar, in particular up to 40 bar, may be preferred.

The amount of water depends on the desired degree of conversion and the process conditions. Generally, the amount of water is per mole of CO in the feedstock₂The adduct fraction is at least 0.1 mole of water. Higher amounts are generally used, e.g. per moleCO₂The adduct fraction is at least 0.2 mol, in particular per mol of CO₂The adduct fraction is at least 0.5 mole water. The maximum value is not critical for the process according to the invention, but too much water would result in unnecessarily large equipment being required. As a general maximum, mention may be made of the amount of CO per mole of cyclic ethylene₂The adduct portion is up to 500 moles, specifically up to 300 moles, more specifically up to 200 moles, in some embodiments up to 100 moles, or up to 50 moles of water.

The reaction time can vary within wide limits, for example at least one minute, in particular at least 5 minutes, more in particular between 15 minutes and 24 hours, depending on the reaction temperature and the desired degree of conversion. In one embodiment, the reaction time may be at least 30 minutes, or at least 1 hour. The reaction time can preferably vary between 1 hour and 12 hours, in particular between 1 hour and 6 hours. When lower temperatures are used, longer reaction times may be required to achieve the desired degree of conversion.

In one embodiment of the invention, the desorption step is carried out by reacting CO of an ethyleneamine compound₂The adduct being in the liquid phase with water at a rate of CO per mole₂The addition product portion 0.1-20 mol of water is reacted at a temperature of at least 230 ℃ and CO is removed₂To proceed with. It has been found that the use of small amounts of water with relatively high temperatures and CO₂The combination of removal results in an efficient process with good conversion and less by-product formation. It has been found that it is possible to use per mole of CO in this embodiment of the process according to the invention₂A relatively limited amount of water of at most 20 moles of water in the adduct fraction gives good conversion. It has been found that it is possible to work with even lower amounts of water, e.g. per mole of CO₂An adduct fraction of water in an amount of up to 15 moles, more particularly per mole of CO₂Water in an amount of up to 10 moles of adduct moieties, or even per mole of CO₂The adduct fraction is at most 5 moles of water.

Per mole of CO₂The range of 0.1 to 20 moles of water of the adduct fraction refers to the total amount of water added during the process, depending on the start of the reactionThe amount of urea fraction in the feed was calculated. To obtain complete conversion, per mole of CO to be converted₂The adduct portion requires 1 mole of water. Since complete conversion is not always required, a smaller amount of water can be used. Thus, the amount of water used is at least per mole of CO₂Adduct fraction 0.1 mol. Higher amounts are generally used, e.g. per mole of CO₂The adduct fraction is at least 0.2 mol, in particular per mol of CO₂The adduct fraction is at least 0.5 mole of water.

Water may be added at the beginning of the desorption step in a single dose. However, it is preferred to add water in multiple doses or continuously during the process. Multiple feed points may be used in continuous operation. 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 by-products.

The molar ratio of water to urea moieties is calculated from the water present in the liquid reaction medium. If the water is added as water vapor, which may be an attractive embodiment of combining the addition of water with the supply of heat to the reaction mixture, a substantial portion of the water in the water vapor is not absorbed by the liquid reaction medium. It is within the scope of the person skilled in the art to adjust the conditions of the water addition process via water vapor in such a way that the desired amount of water is absorbed by the reaction medium. Water may also be present in the feedstock from the start of the reaction, for example, as a result of the process by which the feedstock is produced. Water may also be added as a liquid.

In one embodiment of the desorption step, CO is removed₂. When the conversion of ethylene urea to ethylene amine compounds has been completed, CO may be carried out₂And (5) removing. However, it is preferred to carry out the CO during the reaction₂And (5) removing. CO 2₂Removal may be performed in a manner known in the art. The most basic practice is to empty the reaction vessel. Stripping fluids, especially stripping gases, can be used to increase CO₂And (4) removing rate. Increase of CO₂Other measures of removal rate will be apparent to the skilled person, including such measures as stirring of the reaction mixture, sparging of stripping gas, thin film evaporation, use of packing or trays, etc.

In the case of stripping gas, the flow rate is generally at least 1 cubic meter per 1 cubic meter of reactor volume per hour (at reaction temperature and pressure) and at most 100 cubic meters per 1 cubic meter of reactor volume per hour (at reaction temperature and pressure). The stripping flow rate may be generated by vaporizing the liquid within the reactor vessel, resulting in the in situ generation of a stripping gas. The above ranges also apply to the present embodiment. Of course, it is also possible to combine the addition of the stripping gas with the in situ formation of the stripping gas.

From CO₂Removing the CO-containing gas removed in the step₂May for example comprise from 1 to 99 mol% of CO₂. In other embodiments, the stripping fluid may comprise 1 to 80 mole% CO₂Or 1-60 mol% CO₂. In some embodiments, from CO₂The effluent of the removal step may comprise 1-40 mol% CO₂Or 1-20 mol% CO₂. Lower CO₂The content contributes to the increase of the stripping efficiency, but also requires the use of more stripping gas. Finding the proper balance between these parameters is within the purview of the skilled artisan.

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

The primary amine is an amine-functional compound in which the amine group has the formula R4-NH₂And wherein R4 can be any organic group, preferably an aliphatic hydrocarbon with optional heteroatoms such as oxygen and/or nitrogen. The cyclic secondary amine is an amine 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. Bicyclic tertiary amines are amines of the formula R7-N (-R9) -R8, wherein R7 and R8 together form a hydrocarbon ring optionally having heteroatoms such as oxygen and/or nitrogen, and R7 and R9 together form another hydrocarbon ring optionally having heteroatoms such as oxygen and/or nitrogen. Substituents such as alkyl or hydroxyalkyl may be present on all of the above groups R4 to R9. Primary, cyclic secondary and bicyclic tertiary amines all contain a sterically relatively unblocked amine group. In this context, if one of the amine groups in the compound is a primary or cyclic secondary or bicyclic tertiary amine groupThe compound is then defined as a primary or cyclic secondary or bicyclic tertiary amine, regardless of whether the compound contains other amine groups that may be different in nature. The compound may also contain two or more different amine functions, such as primary and cyclic secondary amine functions, or primary, cyclic secondary and bicyclic tertiary amine functions.

Preferred examples of primary amines are alkylamines, linear ethyleneamines and alkanolamines. Preferred examples of cyclic secondary amines are amines containing a terminal piperazine ring. Preferred examples of bicyclic 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 having more than one amine group, wherein at least one of the amine groups is a primary amine, even more preferably an amine wherein two amine groups are primary amines.

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] octane-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 monocyclic ureas of TEPA and PEHA (i.e., U1TEPA, U2TEPA, U1PEHA, U2PEHA, U3PEHA) and the bicyclic urea isomers of PEHA (i.e., PEHA), Polyethyleneimine (PEI) or ethyleneamine on a solid support.

The amine compound is preferably present in an amount per mole of CO₂The adduct moiety is present in a molar amount of between 0.001 and 100 equivalents, more preferably between 0.01 and 50 equivalents, even more preferably between 0.05 and 30 equivalents, still more preferably between 0.15 and 25 equivalents and most preferably between 0.20 and 20 equivalents.

In the desorption step, CO of the ethyleneamine compound is desorbed₂Conversion of the adduct to CO₂And an ethylene amine compound. Preferably at least 10 mole% of the CO in the system₂Partial conversion of the adduct toThe corresponding ethyleneamine moiety. The maximum will depend on the following desorption and recirculation steps.

Treatment with (strongly) inorganic bases

In one embodiment, the elimination step is performed using a (strong) inorganic base. In the context of the present invention, a strong inorganic base is a base having a material which does not contain a carbon-carbon bond and has a pKb of less than 1.

In one embodiment, the strong inorganic base is selected from metal hydroxides, in particular from hydroxides of alkali metals and alkaline earth 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 metal oxides, in particular from oxides of alkali metals and alkaline earth metals, in particular from calcium oxide, magnesium oxide and barium oxide. The strong inorganic base may preferably be chosen from sodium hydroxide, potassium hydroxide, magnesium (hydr) oxide and calcium (hydr) oxide. It is considered that sodium hydroxide and potassium hydroxide are particularly preferably used. Other strong inorganic bases, such as ammonium hydroxide, may also be used. It will be apparent to the skilled person that mixtures of various inorganic bases may be used. It is also possible to use compounds which, in addition to other components, also comprise a base, provided that the compound is converted into an inorganic base in the reaction medium.

Inorganic base with CO₂The lower limit of the molar ratio of the adduct moieties is not critical. Values of at least 0.2:1 may be mentioned. If desired, CO₂If the adduct is partially completely converted to the corresponding ethyleneamine compound, it may be preferred to use greater amounts, for example in a molar ratio of at least 0.5:1, especially at least 1: 1. It may be preferred to use larger amounts to increase the reaction rate, e.g. inorganic bases with CO₂The molar ratio of the adduct moieties is at least 1.5:1, in particular at least 2: 1.

Inorganic bases are preferred with the CO provided to the product of the inorganic base treatment since large amounts of base do not contribute to further conversion, but instead lead to additional costs₂The molar ratio of the molar amounts of the adduct moieties is at most 20:1, in particular at most 15:1, more in particular at most 10: 1. It has been found that even smaller amounts are possible compared to what is disclosed in the prior artAn inorganic base may be sufficient. More particularly, it has been found that the reaction between an inorganic base and CO₂Good results are obtained with a molar ratio of the 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 CO₂Complete conversion of the adduct moiety and high yield of the resulting ethyleneamine compound. It may be preferred to use each mole of CO₂The adduct fraction uses even less inorganic base, for example in a greater proportion of up to 5:1, in particular up to 4:1, more in particular up to 3: 1. The molar ratio is based on the CO in the feed to the alkaline treatment step₂The molar amount of the adduct moiety.

The treatment with an inorganic base may be carried out, for example, by contacting the material to be treated with a concentrated aqueous inorganic base solution. Depending on the nature of the base and the other constituents of the reaction mixture, it is also possible to add the base in solid form and to dissolve it in the reaction medium. It will be clear to the skilled person that the aim is to bring the base into solution so that the hydroxyl group can react with CO₂The adduct reacts while avoiding unnecessary dilution of the reaction medium.

The reaction may be carried out at a temperature between room temperature and 400 ℃. The temperature and pressure should be chosen such that the reaction mixture is in the liquid phase. Higher temperatures are advantageous because they lead to shorter reaction times. The reaction can preferably be carried out at a temperature of at least 100 ℃, in particular at least 140 ℃, in particular at least 170 ℃. On the other hand, higher temperatures may lead to the formation of undesirable by-products. It may therefore be preferred to carry out the reaction at a temperature of at most 350 ℃ and in particular at most 280 ℃.

Depending on the reaction temperature, the reaction time can vary within wide limits, for example between 15 minutes and 24 hours. The reaction time can preferably vary between 1 hour and 12 hours, in particular between 1 hour and 6 hours. When a smaller amount of base is used, a longer reaction time may be required to obtain the desired degree of conversion.

In one embodiment, the base treatment step from the second reaction sequence may be with a base from the first reaction sequence, as discussed elsewhere hereinAnd combining the physical elimination steps. In this case, the CO due to the ethyleneamine compound₂The conversion of the adduct to the corresponding ethyleneamine compound requires more stringent conditions than the conversion of ethyleneamine hydrohalide to ethyleneamine. Thus, if the two reactions are to be combined in a single step, the conditions and amount of base should be selected such that both reactions occur. CO for reacting ethyleneamines as described above₂The conditions under which the adduct is converted to the corresponding ethyleneamine should be sufficient.

After completion of the reaction, a reaction mixture comprising an ethylene amine compound and a carbonate salt of an inorganic base will be obtained. The salt may be removed by methods known in the art, for example by filtration where the salt is in solid form.

The process according to the invention may be carried out in batch operation, in fed-batch operation or in continuous operation, for example in a continuous flow reactor cascade. Depending on the scale of the operation, it may be preferable to carry out the continuous operation.

Combination of elimination steps

One particular combination of elimination steps includes a desorption step, optionally followed by a separation step in which the desired compound has been removed, followed by treatment with a strong inorganic base.

In one embodiment, the combination comprises converting cyclic ethylene urea to its corresponding ethylene amine by a process comprising:

in a first step, the CO is removed by reacting the cyclic ethylene urea with water in the liquid phase₂Converting the cyclic ethylene urea to its corresponding ethylene amine so as to convert from 5 to 95 mole percent of the ethylene urea moieties in the feedstock to the corresponding amine, and

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

Another specific combination of elimination steps includes a combination of one or more desorption steps with one or more reactive separation steps. The reactive separation comprises CO₂Transfer of the product fromCO of amine compound₂Carbonyl transfer of the adduct to a compound having-NH-CH₂-CH₂-NH-moiety or-NH-CH₂-CH₂-OH moiety or HO-CH₂-CH₂-OH.

In one embodiment, the combination includes converting a cyclic ethylene urea-containing feedstock to its corresponding ethylene amine by a process comprising:

a desorption step in which the CO is removed by reacting the cyclic ethylene urea with water in the liquid phase₂Converting the cyclic ethyleneurea to its corresponding ethyleneamine,

-a reactive separation step, wherein the cyclic ethylene urea is converted to its corresponding ethylene amine by reaction with an amine compound selected from primary or secondary amines having a boiling point higher than the ethylene amine formed during the process.

The reactive separation step may preferably be performed 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 carry out at least two desorption steps, wherein one or more reactive separation steps are carried out therein/therebetween, or at least two reactive separation steps, wherein one or more reactive desorption steps are carried out therein/therebetween.

The reactive separation step may be carried out at any suitable pressure. During the reaction, the pressure in the reactive separation system is preferably at most 127 bar, more preferably at most 50 bar and even more preferably at most 25 bar. Depending on the composition of the reaction medium, lower pressures may be applied, for example less than 15 bar or less than 5 bar. The process may also be carried out at subatmospheric pressure, such as below 700 mbar, more preferably below 100 mbar, even more preferably below 25 mbar, and most preferably below 5 mbar. Typically at a pressure of at least 0.1 mbar.

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

In some embodiments, it is advantageous to combine the reaction step with a separation and/or elimination step at least in part by performing a reactive separation step such as reactive distillation. In the reactive separation step, the above reaction step is carried out under conditions selected so that the CO of the starting compound is₂CO of the adduct to give the product polyethylene amine₂Adducts and, in the same reactive separation, CO of the product polyethyleneamine formed₂The adduct is separated from the other components or its CO portion is transferred in the reactor to another component, which may be the remaining starting compound or by-product.

In one embodiment, the CO of the ethyleneamine compound is reacted by reaction with an amine compound selected from the group consisting of primary or secondary amines having a boiling point higher than the ethyleneamine compound formed during the process₂Converting the adduct to its corresponding ethyleneamine compound, wherein the process is a reactive separation process and the reaction mixture comprises less than 10 wt% water, based on the total weight of the reaction mixture. The reaction may preferably be carried out in less than 7% by weight of the total reaction mixture of water. A pressure of less than 25 bar, in particular less than 500 bar, may be preferred. Typically, the reaction will be carried out at a temperature of at least 150 ℃.

Second reaction sequence

The second reaction sequence comprises the following steps

-in a separation step, the reaction mixture from the amination step is separated into at least two fractions.

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

The reaction of the compound comprising a hydroxyl group with the compound selected from ammonia and the compound comprising an amine group may be represented as a reductive amination reaction. The transfer of an amino group from one molecule to another or within the same molecule can be referred to as a transamination reaction. It will be apparent to the skilled person that both a reductive amination reaction and a transamination reaction will take place in a reactor containing a compound containing a hydroxyl group, such as monoethanolamine, and a compound containing an amino group. Thus, the term amination step will be used in this specification. The term transamination is only used in the specific case where no hydroxyl containing compound is present in the system.

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

The reaction mixture provided to the reaction may contain additional components such as hydroxy functional compounds such as aminoethylethanolamine (AEEA), hydroxyethyl-diethylenetriamine (HE-DEATA), Diethanolamine (DEA) and hydroxyethyl-triethylenetetramine (HE-TETA), and ethylamine compounds such as N-methylethylenediamine (MeEDA), Diethylenetriamine (DETA), piperazine (PIP), N-Aminoethylpiperazine (AEP), triethylenetetramine (TETA), N' -Diaminoethylpiperazine (DAEP), Tetraethylenepentamine (TEPA) and Pentaethylenehexamine (PEHA). These compounds may be provided from external sources or as recycle streams from other steps of the second and first reaction sequences.

The second reaction sequence may also include one or more additional amination steps. In one embodiment, the second reaction sequence includes at least one additional amination step in which an ethylene amine reactant is reacted with a compound selected from ammonia or an additional ethylene amine reactant in the presence of hydrogen and an amination catalyst. In this embodiment, the ethylene amine reactant may be selected from the group consisting of hydroxyl functional compounds and amine functional compounds as described above. Specific embodiments of additional amination steps include:

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

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

It is obvious to the skilled person that in all the mentioned steps further compounds may also be present and that suitable recycling may be applied.

In one embodiment, the process according to the invention comprises at least two amination steps, wherein monoethanolamine is reacted with ammonia in a first amination step to form ethylenediamine and further compounds, and ethylenediamine is reacted in a second amination step in the presence of hydrogen and a catalyst to form higher ethyleneamines, wherein higher ethyleneamines are defined as ethyleneamines comprising more ethyleneic 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 may be supplied to a separation step. While the entire effluent from the first amination step can be supplied to the second step, it is preferred to carry out an intermediate separation step, and in particular to supply EDA to the second amination step. The MEA may be provided to the second amination step, but this is an alternative embodiment.

When the amination reaction involves the reaction of an ethanolamine, such as monoethanolamine or aminoethylethanolamine, with ammonia, the reaction is typically carried out at a temperature in the range of 120-225 ℃. The ammonia is generally added in excess in an amount of at least 3 moles per mole of ethanolamine, in particular at least 5 moles per mole of ethanolamine, more in particular at least 10 moles per mole of ethanolamine. The pressure is generally in the range from 5 to 30MPa, in particular from 10 to 20 MPa.

When ammonia is not present in the amination reaction, the reaction is generally carried out at a temperature in the range of 130-200 ℃ and in particular 140-180 ℃. The pressure is generally in the range from 5 to 40MPa, more particularly in the range from 10 to 20 MPa.

Suitable catalysts for amination are known in the art. Suitable catalysts include catalysts comprising at least one metal component on a porous inorganic support. 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. The selection of suitable amination catalysts and process conditions is within the scope of the skilled person.

Conversion of ethylene oxide and ammonia to monoethanolamine

In one embodiment of the invention, there is a step in the process according to the invention of manufacturing monoethanolamine from ethylene oxide and ammonia. This ethylene oxide conversion step may be present in a second reaction sequence to produce monoethanolamine that is provided to the amination step. It may also be present in the first reaction sequence to provide monoethanolamine to the addition step or chain extension step. In a preferred embodiment of the invention, monoethanolamine from the ethylene oxide conversion step is provided to both the first reaction sequence and the second reaction sequence as this allows a wide range of products to be manufactured using widely available starting materials (ethylene oxide and ammonia).

The reaction of ethylene oxide with ammonia may produce dihydroxyethylene amine (DEA) as a by-product. In one embodiment of the present invention, the DEA produced in the ethylene oxide conversion step is provided to the addition step or chain extension step of the first reaction sequence where it can be used as a starting material for the reaction with the ethyleneamine compound to produce higher ethyleneamines.

The reaction of ethylene oxide with ammonia to form monoethanolamine is known in the art. Typically, the ethylene oxide and ammonia are reacted in the condensed phase at a temperature of 20 to 250 ℃, with a pressure sufficient to maintain the components in the condensed phase. The ammonia is generally provided in excess, with a molar ratio of ammonia to ethylene oxide, for example, in the range of 10:1 to 80: 1. The ammonia may be provided in anhydrous form or in aqueous solution. In one embodiment, especially when the ammonia is provided in anhydrous form, an acid catalyst, especially a solid acid catalyst, may be present. Since the process for the manufacture of monoethanolamine from ethylene oxide and ammonia is known in the art, further description is not required herein.

Ligation of the first and second reaction sequences

In the method according to the invention, the first reaction sequence is linked to the second reaction sequence such that at least one of the following occurs:

-combining steps from the first reaction sequence with steps from the second reaction sequence, or

There are numerous ways in which a first reaction sequence may be linked to a second reaction sequence.

In one embodiment of the invention, the product from the amination step in the second reaction sequence is supplied directly to the addition step or reaction step in the first reaction sequence or in the case of an intermediate separation step.

This embodiment is considered advantageous because it allows the low molecular weight ethyleneamine compound fractions produced in the second reaction sequence (e.g., AEEA, PIP, DETA, and EDA) to be used as starting materials for the production of higher molecular weight ethyleneamine compounds by the process of the first reaction sequence.

This embodiment may be particularly advantageous in case EDA, DETA and/or AEEA generated in the amination step is provided to the addition step or the 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 from the second reaction sequence) as starting materials for the first reaction sequence. This makes it possible to prepare a wide variety of products from widely available and inexpensive starting materials. This embodiment combines the advantages of both reaction sequences, because: the first reaction sequence makes it possible to obtain a higher ethyleneamine product, but does so less effectively with ammonia as the starting material, while the second reaction sequence may use a combination of MEA and ammonia as the starting material, but has been found to be less selective when the goal is to produce a higher ethyleneamine product.

Furthermore, connecting the two reaction sequences in this way allows for increased flexibility in product variety by allowing the output to be shifted from less demanding products to more demanding products. Fig. 1 and 2A show one way of carrying out this embodiment. A variation of this embodiment is depicted in fig. 5.

In one embodiment of the invention, the product from the amination step and the product from the elimination step are combined and provided to a separation step. Various ways of combining the separation steps can be considered, ranging from combining all products of two reaction sequences, combining all products of one reaction sequence with partial products of another reaction sequence to combining partial products of one reaction sequence with partial products of another reaction sequence. Generally, from an operational perspective, combining the separation steps increases efficiency in terms of both equipment costs and operational costs. One way of carrying out this embodiment is shown in fig. 2. Another way of carrying out this embodiment is shown in fig. 3. In general, from a cost perspective, combining the separation steps may be effective, while separating them allows for separation under optimized conditions, which may improve process efficiency.

In one embodiment, the product from the chain extension 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 as it allows for increased process flexibility, which is attractive for the reasons mentioned above. One way of implementing this embodiment is shown in FIG. 2B (

pipelines

405, 406, respectively).

In one embodiment, the product from the elimination step or the separation step (if present) of the first reaction sequence is provided to the amination reaction. Again, this is advantageous as it allows for increased process flexibility, which is attractive for the reasons mentioned above. One way of implementing this embodiment is shown in FIG. 2B (

lines

407, 408, respectively).

In one embodiment of the invention, the elimination step in the first reaction sequence comprises a distillation step, and the product from the amination step is provided to the distillation step in the elimination step. This embodiment allows combining the various separation steps into a single unit. This helps to improve operating efficiency and reduce capital Costs (CAPEX) and operating costs (OPEX).

In one embodiment of the invention, the second reaction sequence comprises at least one additional amination step wherein an ethylene amine reactant is reacted with a compound selected from ammonia or an additional ethylene amine reactant in the presence of hydrogen and an amination catalyst.

In particular, the additional amination step comprises an amination step selected from the group consisting of 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 which at least two amination steps are included in the second reaction sequence, wherein monoethanolamine is reacted with ammonia in the first amination step to form ethylenediamine, and ethylenediamine is reacted in the second amination step in the presence of hydrogen and an amination catalyst to form higher ethyleneamines, wherein higher ethyleneamines are defined as ethyleneamines comprising more ethyleneic moieties than ethylenediamine.

In one embodiment of the invention, the product from the further amination step in the second reaction sequence is combined with the product from the elimination step in the first reaction sequence and supplied to the separation step. This embodiment allows combining the individual separation steps in a single unit. This helps to improve operating efficiency and reduce capital Costs (CAPEX) and operating costs (OPEX).

In one embodiment of the invention the product from the first reaction sequence and the product from the second reaction sequence are provided to a single purification step. Combining these steps allows for more efficient use of equipment while reducing associated costs.

In one embodiment, the process further comprises an ethylene oxide conversion step, wherein ethylene oxide is reacted with ammonia to produce monoethanolamine, and monoethanolamine is provided to one or more of an amination step, an addition step, or a chain extension reaction step. The use of monoethanolamine from the reaction of ethylene oxide with ammonia allows the use of inexpensive, widely available starting materials and the presently claimed method is a flexible way of utilising this material. In this way, higher ethyleneamines can be obtained from ethylene oxide and ammonia without the need to provide other EDA compounds. In one embodiment, the process of the present invention comprises the step of reacting ethylene oxide with ammonia to form monoethanolamine, wherein a first portion of monoethanolamine is provided to an amination step in a second reaction sequence where it reacts with ammonia to form EDA, which is provided at least in part to an addition step or a chain extension step of the first reaction sequence, and wherein a second portion of monoethanolamine is provided to an addition step or a chain extension step of the first reaction sequence. This embodiment allows all ethyleneamine and ethanolamine starting materials to be obtained from ammonia and ethylene oxide without the need to add ethyleneamine or ethanolamine compounds from other sources.

The drawings of the present application show various ways in which this may be achieved. It is obvious to the person skilled in the art that various ways of connecting sequences can be combined, even if these ways are provided in different figures.

The present invention will be elucidated with reference to the following figures, without being limited thereto. The following applies to all processes and figures given herein:

there may be intermediate separation steps, even if not explicitly stated or shown;

the effluent from a process step may be partially or totally supplied to other process steps, whether or not after having been subjected to an intermediate separation step;

the starting materials or intermediates may be suitably recovered even if not explicitly stated or shown;

purge and make-up flows may be present, even if not explicitly specified or shown;

the reactants may be provided separately or in combination, even if not explicitly stated or shown;

the different steps in the figures do not necessarily refer to different units or reactors;

embodiments of the invention may be combined unless they are mutually exclusive;

elements of the drawings may be combined, and as is apparent from the description, not all illustrated elements may be essential to a particular embodiment;

sometimes the reaction stream is indicated by the abbreviation ethyleneamine compound. The expression should not be interpreted as a limitation of the content of the fractions, which may also comprise other compounds, for example ethanolamine compounds, if present, or CO adducts of ethyleneamines or ethanolamine compounds, if present, as is apparent to the skilled person.

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

In FIG. 1, via line 1 will contain-NH-CH₂-CH₂-NH-moiety or-NH-CH₂-CH₂-OH moiety or HO-CH₂-CH₂The starting compound of-OH is supplied to addition step 2, where a carbon oxide delivery agent, for example CO, is added via line 3₂Or another carbon oxide delivery agent. Of course, the CO adduct may also be provided in other ways as described herein, for example by CO transfer. The adduct is supplied to the chain extension reaction step 5 via line 4. Additional reactants may be provided to the chain extension reaction step 5 through lines not shown. For example, if the product from the addition step is the CO of an ethyleneamine compound₂Adduct the ethanolamine compound may then be provided to the chain extension reaction step 5. The effluent from the amplification reaction step 5 is supplied via line 6 to the elimination step 7. In CO₂In the elimination step 7, CO of the ethylene amine compound is eliminated₂Conversion of the adductWhich is the corresponding ethyleneamine compound, is withdrawn via line 9. CO is withdrawn from the product ethyleneamine compound via line 10₂A carbonyl-containing compound eliminated from the adduct. Although not essential to the invention, fig. 1 also comprises a separation step 14 provided after the elimination step 7. The separation step 14 results in the separation of the different fractions. For example, starting materials and/or intermediate compounds can be removed via line 16. If so is desired, they may be supplied to the addition step 2 and/or the chain extension reaction step 5 through a line not shown. The separation step 14 also produces a product fraction of the higher ethyleneamine compound that is withdrawn via line 15. This part of the figure thus illustrates the first reaction sequence.

In the second reaction sequence, monoethanolamine is supplied to the amination step 200 via line 201. Ammonia may be provided via line 202 and hydrogen may be provided via line 203. The product mixture from the amination reaction 200 is supplied to a separation step 205 via line 204. The separating step produces at least two fractions. In the embodiment shown in this figure, recycle stream 206 recycles ammonia and optionally hydrogen to amination reactor 200. A product stream comprising ethyleneamine is withdrawn from the process via line 207. The separation step 205 may produce more than the two fractions specified herein. All fractions can be processed as desired. For example, product fraction 207 may be sent to additional separation or purification steps not shown. The same is true for the other fractions. Line 401 will contain a compound having-NH-CH₂-CH₂-NH-moiety or-NH-CH₂-CH₂The fraction of ethyleneamine or ethanolamide compounds of the-OH moiety is supplied to the addition step 2. Examples of suitable compounds are in particular monoethanolamine and ethylenediamine, but higher molecular weight compounds can also be provided. Line 402 provides a fraction comprising an ethyleneamine or ethanolamin compound to the chain extension step 6. The composition of these 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 the

fractions

401 and 402. In one embodiment, the fraction comprises cyclic compounds such as piperazine or aminoethylpiperazine, which are further processed in a first reaction sequenceThis can then lead to the formation of higher ethyleneamine compounds containing piperazine rings, such as Piperazinoethylenediamine (PEEDA), diaminoethylpiperazine, and piperazine ring-containing pentaethyleneamines and hexaethyleneamines.

The embodiment of fig. 1 is believed to be advantageous because it allows the low molecular weight ethyleneamine compound fractions produced in the second reaction sequence, such as AEEA, PIP, DETA and EDA, to be used as starting materials in the production of higher molecular weight ethyleneamine compounds by the process of the first reaction sequence.

This embodiment may be particularly advantageous when EDA produced in the amination step 200 is provided to the addition step 2 or the chain extension reaction step 5. In this 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 from the second reaction sequence) as starting materials for the first reaction sequence. This makes it possible to prepare a wide variety of products from widely available and inexpensive starting materials. A variation of this embodiment is depicted in fig. 5.

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

Fig. 2 shows the same entities as fig. 1. However, unlike

lines

401 and 402 present in fig. 1, a fraction is taken from the elimination step 7 in fig. 2 via line 403 and provided to the separation step 205. The fraction from the separation step 404 of the first reaction sequence may be provided to the separation step 205 of the second reaction sequence via line 404. It will be clear to the skilled person that it is also possible to have only one of the

fractions

403 and 404.

This embodiment allows for an efficient and cost-effective customization of the separation step. Furthermore, the method allows to provide compounds, in particular low molecular weight compounds such as MEA, EDA, DETA, AEEA and PIP, which may be present in the reaction mixture formed in the first reaction sequence to be processed in the second reaction sequence in a highly efficient manner. In fig. 2, these fractions are provided to separation step 205 via line 404, where they can be part of the recycle fraction provided to amination step 200 via line 206. The fraction originating from the separation step 14 can also be supplied to the amination step 200 via a line not shown.

Fig. 2A shows a preferred embodiment of the invention, in which all

lines

401, 402, 403 and 404 are present. The figure is thus illustrative of a preferred embodiment of the invention, wherein the first reaction sequence and the second reaction sequence are linked such that:

-the ethyleneamines produced in the second reaction sequence are supplied to the absorption step and/or the chain extension step in the first reaction sequence, and

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

This combination of providing one or more fractions from the fractionation steps in the second reaction sequence to the first reaction sequence and vice versa allows a particularly efficient use of the equipment and makes it possible to tailor the properties of the produced product to market requirements. There may be one or both of the streams shown as 401 and 402 and one or both of the streams shown as 403 and 404.

Fig. 2B shows another embodiment of the present invention. In addition to the

lines

401, 402, 403, and 404 of FIG. 2A, FIG. 2B includes the following lines:

405 an ethylene amine compound from the chain extension step to the amination step;

406 ethylene amine compound from the chain extension step to the separation step;

407 ethylene amine compound from elimination step to amination step;

408 ethylene amine compound from the first sequence of separation steps to the amination step.

It will be obvious to the skilled person that it is not necessary to combine all these lines. However, this is of course possible. It is within the purview of the skilled artisan to select what stream best matches the desired product characteristics while taking into account the available starting materials.

Figure 3 shows an embodiment of the invention in which the steps of the first reaction sequence and the steps of the second reaction sequence are combined. More specifically, the effluent from the elimination step 7 and the effluent from the amination step 200 are both provided to the separation step 208. In the separation step 208, many different streams are generated, examples of which are shown in FIG. 3. A first fraction comprising ammonia and optionally hydrogen is withdrawn via line 209. If so is desired, this fraction may be recycled in whole or in part to the amination step 200. Additional fractions containing relatively light components such as monoethanolamine and diethanolamine are withdrawn via line 210. This fraction may be provided in whole or in part to one or more of the amination step 200, the addition step 2 or the chain extension reaction step 5, depending on the composition of the fraction, the target product and the available starting materials. A product fraction containing compounds targeted to one or more of, for example, Diethylenetriamine (DETA), triethylenetetramine (TETA), and Tetraethylenepentamine (TEPA) may be withdrawn via line 211. Fractions containing higher boiling compounds, for example compounds still containing cyclic urea moieties, can be withdrawn via line 212. It will be apparent to the skilled person that more or fewer streams may be generated by the separation step 208. The four streams discussed herein are examples only.

The use of a combined separation section as shown in this embodiment enables a more efficient use of the separation equipment and an efficient tailoring of the product fractions to the prevailing market conditions.

Fig. 4 shows a variant of fig. 1, in which a transamination step 213 has been included. In this embodiment, an effluent stream comprising EDA is withdrawn from the separation step 205 via line 214 and provided to the transamination step 213 where it reacts in the presence of a catalyst in contact with hydrogen provided via line 215. It will be apparent to the skilled person that hydrogen need not be provided through a separate line. It can also be introduced in said step in combination with other streams. The same applies to the supply of hydrogen to the amination step 200. The hydrogen streams in the process according to the invention may be from the same or different sources. The hydrogen can be recycled as required. Monoethanolamine may be supplied through a line not shown. The reaction product comprising higher ethanolamine is supplied via line 216 to separation step 205.

In the embodiments described herein, the effluents from the amination step 200 and the transamination step 213 are each coupled to the separation step 205, respectively. It is obvious to the skilled person that the amination step, the separation step, the transamination step and the further separation step can also be performed in sequence.

It is also clear to the skilled person that effluents comprising EDA from other sources may also be provided to the transamination step. Examples include streams comprising EDA from the chain extension reaction step, the elimination step and the separation step.

The process of this embodiment comprising two amination steps enables the production of increased amounts of higher ethylene amine compounds in a controlled and efficient manner. Furthermore, the presence of two amination steps in the second reaction sequence in combination with the first reaction sequence increases process flexibility because of the ability to make higher ethyleneamines (which are produced primarily in the chain extension step of the first reaction sequence and the second amination step of the second reaction sequence) on demand can be increased.

Fig. 5 shows another embodiment of the present invention, which further comprises an ethylene oxide conversion unit 217. In ethylene oxide conversion unit 217, ethylene oxide provided via line 218 is reacted with ammonia provided via line 219 to form monoethanolamine. Monoethanolamine may be provided as a starting material to the amination step 200 via line 201. It can also be supplied to the addition step 2 via line 1 or to the chain extension reaction step 5 via line 220 as desired. The ammonia from line 219 can be from the same source as the ammonia provided via line 202, or from a different source. It may also come from the separation step 205 via a line not shown.

In this embodiment, streams 401 and 402 are not necessary, but their presence is advantageous for the reasons discussed above with respect to fig. 1. The use of ammonia and ethylene oxide shown in this figure can be advantageously combined with the recycling of compounds through one or more of

lines

401, 402, 403, 404, 405, 406, 407, and 408 as shown in figures 2A and 2B. It will be obvious to the skilled person that it is not necessary to combine all these lines. However, this is of course possible. It is within the purview of the skilled artisan to select what stream best matches the desired product characteristics while taking into account the available starting materials.

The embodiment of the invention shown in fig. 5 allows for the use of ammonia and ethylene oxide as starting materials for a variety of high value ethyleneamine products.

List of reference numerals

1 comprises-NH-CH₂-CH₂-NH-moiety or-NH-CH₂-CH₂-OH moiety or HO-CH₂-CH₂-OH starting Compound

2 addition step

3 carbon oxide delivery agents, e.g. CO₂

4 effluent from the addition step

5 chain extension reaction step

6 effluent from the chain extension reaction step

7 Elimination step

9 ethyleneamine compounds

10 Compounds comprising a carbonyl group

14 separation step

15 ethylene Compound product fraction

16 starting materials and/or intermediates

200 amination step

Provision of 201 monoethanolamine

202 Ammonia

203 hydrogen gas

204 product mixture from the amination step

205 separation step

206 recycle stream of ammonia and optionally hydrogen

207 product stream

208 separation step

209 comprises a fraction of ammonia and optionally hydrogen

210 fraction comprising light components

211 product fraction

212 fraction containing high-boiling components

213 transamination step

214 an effluent stream comprising EDA

215 hydrogen gas

216 product of the transamination step

217 ethylene oxide conversion unit

218 ethylene oxide

219 Ammonia

220 MEA401 ethyleneamine Compound to addition step

402 ethyleneamine compound to the chain extension reaction step

403 ethylene amine compound from elimination step to separation step

404 ethylene amine compound from the first sequence of separation steps to the second sequence of separation steps

405 ethylene amine compound from chain extension step to amination step

406 ethylene amine compound from chain extension step to separation step

407 Ethylene amine Compound from Elimination step to amination reaction step

408 ethylene amine compound from the first sequence of separation steps to amination reaction step

Claims

1. A process for the manufacture of an ethyleneamine compound selected from the group consisting of ethyleneamines and hydroxyethylethyleneamines, wherein the process comprises two reaction sequences,

the first reaction sequence comprises the following steps

the second reaction sequence comprises the following steps

-in a separation step, the reaction mixture from the amination step is separated into at least two fractions,

2. The process of claim 1, wherein the product from the amination step is provided directly to or with an intermediate separation step to an addition step or a reaction step in the first reaction sequence.

3. The process of any one of the preceding claims, wherein the product from the amination step and the product from the elimination step are combined and provided to a separation step.

4. The process according to any one of the preceding claims, wherein the elimination step in the first reaction sequence comprises a distillation step and the product from the amination step is provided to the distillation step in the elimination step.

5. The process of any of the preceding claims, wherein the second reaction sequence comprises at least one additional amination step wherein an ethylene amine reactant is reacted with a compound selected from ammonia or an additional ethylene amine reactant in the presence of hydrogen and an amination catalyst.

6. The process of claim 5, wherein the additional amination step comprises a step selected from the group consisting of:

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

7. The process of claim 4 or 5, wherein the second reaction sequence comprises at least two amination steps, wherein monoethanolamine is reacted with ammonia to form ethylenediamine in the first amination step and ethylenediamine is reacted in the second amination step in the presence of hydrogen and a catalyst to form higher ethyleneamines, wherein higher ethyleneamines are defined as ethyleneamines comprising more ethyleneic moieties than ethylenediamine.

8. The process of claim 7, wherein EDA from the first amination step is provided as starting material either directly to the second amination step or from an intermediate separation step.

9. The process according to any one of claims 4-8, wherein the product from the further amination step and the product from the elimination step are combined and provided to a separation step.

10. The process according to any one of claims 4-9, wherein the elimination step in the first reaction sequence comprises a distillation step and the product from the further amination step is provided to the distillation step in the elimination step.

11. The method of any one of the preceding claims, wherein the product from the first reaction sequence and the product from the second reaction sequence are provided to a single purification step.

12. The process of any one of the preceding claims, wherein the process further comprises an ethylene oxide conversion step, wherein ethylene oxide is reacted with ammonia to produce monoethanolamine, and monoethanolamine is provided to one or more of the following steps:

-an amination step in which the amine is removed,

-an addition step of the reaction mixture,

-a chain extension reaction step.

13. The process according to any one of the preceding claims, wherein the ethylenediamine or aminoethylethanolamine produced in the amination step is provided directly to or with an intermediate separation step to an addition step or a reaction step in the first reaction sequence.

14. The method of any preceding claim, wherein the product from the chain extension 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.

15. The process according to any one of the preceding claims, wherein the product of the elimination step or, if present, the separation step from the first reaction sequence is provided to an amination reaction.

16. The method according to any one of the preceding claims, comprising the step of reacting ethylene oxide with ammonia to form monoethanolamine, wherein a first portion of monoethanolamine is provided to an amination step in a second reaction sequence where it reacts with ammonia to form EDA, which is provided at least in part to an addition step or a chain extension step of the first reaction sequence, and wherein a second portion of monoethanolamine is provided to an addition step or a chain extension step of the first reaction sequence.