WO2006114417A2 - Method for the production of ethyleneamines - Google Patents

Abstract

Disclosed is a method for producing ethyleneamines, in which ethylene oxide (EO) is continuously reacted with ammonia on an inorganic ion exchanger as a heterogeneous catalyst in anhydrous conditions in a first reaction stage, the obtained reaction product containing monoethanolamine (MEOA), diethanolamine (DEOA), and triethanolamine (TEOA) at a weight ratio MEOA: DEOA: TEOA = 80 - 94: 5.9 - 15: 0.1 - 5, and the reaction product is then continuously reacted with ammonia in the presence of hydrogen and a heterogeneous hydrogenation catalyst in a second reaction stage.

Description

Process for the preparation of ethylene amines

description

The present invention relates to a process for the production of ethylene amines.

Ethyleneamines are used as solvents, stabilizers, for the synthesis of chelating agents, resins, drugs, inhibitors and surfactants.

Numerous methods have been described in the literature for the production of ethylene amines.

For the preparation of monoethanolamine from ethylene oxide:

WO-A1-01 / 94290 (BASF AG) discloses a process for the preparation of alkanolamines from alkylene oxide and ammonia, wherein a controlled control of the temperature in the reaction space.

EP-A2-1 291 339 (BASF AG) relates to a continuous process for the preparation of monoethanolamine, diethanolamine and triethanolamine by reacting ammonia and ethylene oxide in the liquid phase in the presence of water as catalyst in a pressure column.

DE-A-1 941 859 (Mo Och Domsjö Aktiebolag) (US equivalent 3,697,598) relates to a continuous process for the preparation of monoalkanolamines from an alkylene oxide and ammonia in the presence of a cation exchange resin catalyst.

EP-A1-652 207 (Nippon Shokubai) describes a process for preparing an alkanolamine by reacting an alkylene oxide with ammonia in the liquid phase in the presence of a catalyst comprising a rare earth element on an inorganic heat-resistant support (eg phyllosilicate) ,

The processes according to DE-A-1 941 859 and EP-A1-652 207 are examples of highly selective ethylene oxide reactions with NH ₃ to monoethanolamine. Catalyst is not water here. Both methods allow an ethanolamine product stream with a weight ratio of ethanolamines of> 90 MEOA: 9-10 DEOA: <1 TEOA.

For the production of ethylene amines from ethylene dichloride or monoethanolamine:

The ethylene dichloride (EDC) process involves the chlorination of ethylene and subsequent reaction with ammonia. Disadvantage of the implementation is the comparison wise costly functionalization by reaction with chlorine, associated with an inevitable salt attack in the substitution with ammonia. Subsequently, the neutralization with sodium hydroxide to release the ethyleneamines is inevitable.

Alternatively, a reaction of monoethanolamine and ammonia to amination catalysts takes place in the presence of hydrogen. Raw material base is also ethylene, which is first functionalized to ethylene oxide. The opening of the epoxide with ammonia provides a mixture of mono-, di- and triethanolamine, which is separated by distillation into the individual components. Monoethanolamine (MEOA) is then by amination in a mixture of ethylenediamine (60- 80 wt .-%), Diethylentria- min (5-15 wt .-%) and higher linear polyethyleneamines in addition to piperazine and piperazine derivatives (5-15 wt .-%) as cyclic secondary products. In addition, by-product aminoethylethanolamine (AEEA, 5-15% by weight) is obtained by intermolecular reductive amination of two MEOA units.

EP-A2-146 508 (Berol Kemi AB) relates to specific Ru catalysts and their use in processes for the amination of alkanolamines.

EP-A2-839 575 (BASF AG) describes Ru catalysts for the amination of alcohols, such. Monoethanolamine.

WO-A-05/014523 (BASF AG) relates to a process for the preparation of ethyleneamines by reacting monoethanolamine (MEOA) with ammonia in the presence of a catalyst in a reactor (1) and separating the resulting reaction output, wherein obtained in the separation Ethylenediamine (EDA) is reacted in a separate reactor (2) in the presence of a catalyst to diethylenetriamine (DETA) and the resulting reaction effluent is fed to the separation of the reaction effluent resulting from reactor 1.

For the production of ethylene amines from ethylene oxide:

US-A-3,597,483 (BASF AG) relates to the direct preparation of 1, 2-diamines by reaction of 1, 2-epoxides with ammonia, primary or secondary amines in the presence of water, hydrogen and a hydrogenation catalyst.

DD-A-149 509 (VEB Leuna-Werke) describes a process for the preparation of polyethylenepolyamines directly from ammonia and ethylene oxide by reaction in a staggered temperature pressure reactor for the uncatalyzed reaction of ammonia with ethylene oxide and for the metal-catalyzed amination of Monoethanolamine. The reaction product is a polyamine mixture. EP-A 1-75 940 and EP-A1-75 941 (both UCC) relate to the preparation of ethylenediamine or polyethylene polyamines by reacting ethylene oxide with ammonia and subsequent amination of the resulting ethanolamines.

The procedures involve the recycling of unreacted MEOA after separation from the monoethanolamine (MEOA) amination product mixture to the amination reactor to ensure sufficient excess of MEOA for amination to drive back amination of the co-products DEOA and TEOA. Although this makes it possible to achieve a sufficient conversion of the fresh MEOA supplied, the quantities of the secondary components DEOA and TEOA produced are not reduced. The space-time yield of the MEOA reaction decreases and the amination of DEOA and TEOA can not be completely suppressed.

A scheme for the production of ethylene amines according to the conventional intermediate isolation methods of MEOA is given in Appendix 1.

According to the invention it has been recognized that the conventional water-catalyzed NH ₃ -EO reaction provides only a kinetically controlled MEOA, DEOA, TEOA mix with a very high proportion of DEOA and TEOA. Even with NH ₃ / EO molar ratios up to 40: 1, maximum product mixtures comprising MEOA, DEOA and TEOA in the weight ratio 70 - <80: 10 - 20: 2-5 are obtained by conventional processes.

Since the coupling products DEOA and TEOA are not inert in the amination stage, these by-products are an additional burden on the amination catalyst and, in particular triethanolamine, inferior products are formed which can only be utilized as high-boiling amine mixtures.

The amination of diethanolamine with NH ₃ provides with AEEA, piperazine and little DETA Although known products of Ethylenaminmixes. However, in particular the demand for AEEA and PIP is at a significantly lower level compared to EDA and DETA, so that easily unusable surpluses can occur here.

The present invention has for its object, overcoming one or more disadvantages of the prior art, to find an improved economical process for the production of ethylene amines. The process should be based on the starting material ethylene oxide and an intermediate isolation of monoethanolamine should not take place. The process should provide especially ethylenediamine with high space-time yield and selectivity and the catalysts have a long service life.

[Space-time yields are given in 'product quantity / (catalyst volume • time)' (kg / (l _cat . • h)) and / or, product quantity / (reactor volume • time) '(kg / (l _rea kto _r • H)]. Accordingly, a process for the preparation of ethylene amines has been found which is characterized in that in a first reaction stage ethylene oxide (EO) is continuously reacted with ammonia under anhydrous conditions on an inorganic ion exchanger as heterogeneous catalyst, the resulting reaction product monoethanolamine (MEOA), Diethanolamine (DEOA) and triethanolamine (TEOA) in the weight ratio MEOA: DEOA: TEOA = 80-94: 5.9-15: 0.1-5, and the reaction product is then continuously in a second reaction stage with ammonia in the presence of Reacting hydrogen and a heterogeneous hydrogenation catalyst.

The ethyleneamines are, in particular, ethylenediamine (EDA), diethylenetriamine (DETA), aminoethylethanolamine (AEEA), piperazine (PIP) and / or triethylenetetramine (TETA).

Surprisingly, no deterioration in the performance (catalyst lifetime, selectivity, space-time yield) is observed in the process of the invention in the amination stage compared to an amination of previously isolated MEOA.

Also occur in the amination no problems due to any existing catalyst abrasion from the EO reactor of the first reaction stage. The by-product spectrum of heterogeneously catalyzed EO conversion also proves to be unproblematic for the performance of the amination stage.

Advantages of the process according to the invention are also achieved in the investment since water and ammonia columns and MEOA columns of an upstream ethanolamine process can be dispensed with if the effluent from the ethanolamine synthesis (1st reaction stage) is passed directly to the amination reactor (2nd reaction stage ) leads.

In addition, there are savings in energy costs, since in the ethoxylation used in excess NH _{3 is} preferably not removed by distillation and MEOA must not be distilled before the amination pure.

The procedure can be carried out as follows.

Ethylene oxide (EO) is continuously fed together with ammonia into a reactor, preferably tubular reactor. The molar ratio of EO to NH ₃ is preferably in the range from 1:10 to 30, in particular from 1:15 to 29, especially from 1:20 to 28, very particularly from 1: 23 to 27, for example from 1:25. The heterogeneous catalyst is an inorganic ion exchanger. The catalyst is preferably arranged in the reactor as a fixed bed.

The inorganic ion exchanger is preferably a silicate, in particular a framework silicate and / or sheet silicate, e.g. as described in the "Textbook of Inorganic Chemistry" (Holleman-Wiberg), 91st-100th Edition, 1985, at pages 771-778.

Particular preference is given to using an aluminosilicate as the framework and / or layered silicate.

Preferred examples of framework silicates are feldspars and zeolites. Preferred examples of sheet silicates are clay minerals such as bentonite, montmorillonite (e.g., K10) or saponite.

The inorganic ion exchanger is preferably used as a shaped body. For shaping, all known and / or suitable kneading and shaping devices or methods can be used. Among others, these include:

(i) Briquetting, i. mechanical pressing with or without the addition of additional binder material;

(ii) pelleting, i. Compacting by circular and / or rotating motions; (iii) sintering, i. the material to be deformed is subjected to a thermal treatment.

For example, the shaping may be selected from the following group, the combination of at least two of these methods being explicitly included: briquetting by stamping presses, roll pressing, ring roll pressing, briquetting without binder;

Pelletizing, melting, spinning techniques, deposition, foaming, spray-drying; Burning in the shaft furnace, convection oven, traveling grate, rotary kiln, rumbling.

The proportion of the inorganic ion exchanger in the catalyst molding is preferably at least 5 wt .-%, in particular at least 10 wt .-%, particularly preferably at least 50 wt .-%.

The pore volume of the shaped catalyst bodies for pores having diameters in the range from 2 nm to 10 μm, measured by means of Hg porosimetry according to DIN 66134, is preferably in the range from 0.1 to 1.5 cm ³ / g, particularly preferably in the range from 0.3 to 1.0 cm ³ / g. The reaction of the ethylene oxide to MEOA, DEOA and TEOA provides particularly favorable product mixtures for the subsequent amination of the alcohol when it is carried out on a scandium, yttrium and / or lanthanide-doped catalyst molding.

In a particularly preferred embodiment, therefore, the shaped body contains one or more metals in the oxidation state III, selected from scandium, yttrium and / or the lanthanides (such as lanthanum, cerium, praseodymium, neodymium, samarium, europium, gadolium, terbium, dysprosium, Holmium, erbium, thulium, ytterbium, lutetium).

The proportion by weight of o.g. Overall, metals are preferably in the range from 0.5 to 50% by weight, in particular from 1 to 30% by weight, in particular from 7 to 15% by weight (in each case based on the silicate weight).

The reaction is preferably carried out at an absolute pressure in the range of 50 to

150 bar, especially 90 to 110 bar, and preferably at a temperature in the range of

70 to 18O ⁰ C, especially 80 to 12O ⁰ C.

The LHSV of the reactor is preferably in the range of 5 to 15 I / 1 (catalyst) ^• h, in particular in the range of 7 to 12 1/1 _(K ata ysator _l) * h.

By adjusting the temperature in o.g. Area a complete conversion of the ethylene oxide is ensured.

The resulting reaction product (= the reactor effluent of the first reaction stage) contains monoethanolamine (MEOA), diethanolamine (DEOA) and triethanolamine (TEOA) in the weight ratio MEOA: DEOA: TEOA = 80-94: 5.9-15: 0.1-5, preferably in the weight ratio 85 - 94: 5.9 - 13: 0.1 - 4, eg in the weight ratio MEOA: DEOA: TEOA = 90: 9: 0.3.

Typical weight ratios are, depending on the NH ₃ : EO molar ratio (MV) used:

(LHSV = liquid hourly space velocity, unit: h ^"1 ) The reactor is, preferably without relaxation and preferably without cooling, with hydrogen (eg 0.01 to 10 wt .-% based on the total feed) and in a second reactor, preferably tubular reactor, driven. Optionally, a mixing section can be installed in front of the second reactor.

The heterogeneous hydrogenation catalyst in the second reaction stage preferably contains one or more metals selected from Ni, Co, Cu, Ru, Re, Pd and / or Pt on a support selected from Al ₂ O ₃ , TiO ₂ , ZrO ₂ and / or SiO ₂ . The catalyst is preferably arranged in the reactor as a fixed bed.

Particularly preferred catalyst is an amination catalyst, for example a catalyst containing Ni, Co and Cu on an oxidic support, such as Al ₂ O ₃ , ZrO ₂ , SiO ₂ .

In a preferred embodiment, catalysts used in the second reaction stage are the catalysts disclosed in DE-A-19 53 263 (BASF AG) containing cobalt, nickel and copper and aluminum oxide and / or silicon dioxide having a metal content of from 5 to 80% by weight %, in particular 10 to 30 wt .-%, based on the total catalyst, wherein the catalysts, calculated on the metal content, 70 to 95 wt .-% of a mixture of cobalt and nickel and 5 to 30 wt .-% copper and wherein the weight ratio of cobalt to nickel 4: 1 to 1: 4, in particular 2: 1 to 1: 2, for example, the catalyst used in the examples there with the composition 10 wt .-% CoO, 10 wt. % NiO and 4 wt.% CuO on Al ₂ O ₃ .

The reductive amination is preferably carried out at an absolute pressure in the range of 150 to 250 bar, in particular 170 to 220 bar, and preferably at a temperature in the range of 160 to 22O ⁰ C, especially 170 to 21O ⁰ C.

If the connection between the reactors of the two reaction stages is sufficiently isolated, preheating before the second reactor stage is not necessary. However, the reaction can be run within the described reaction temperatures at freely selectable temperature differences between the first and second reactor.

A metered addition of NH ₃ before the second reactor stage is not necessary to produce a customary product mixture of ethylene amines (ethylenediamine, diethylenetriamine, piperazine, aminoethylethanolamine, diethanolamine, triethanolamine, etc.), but can optionally be used to increase the proportion of lower ethyleneamines (ethylenediamine, diethylenetriamine). be performed.

The amination of the MEOA-DEOA-TEOA mixture from the EO reaction of the first reaction stage is preferably not driven to the full conversion of the three ethanolamines in order to increase the proportion of linear, lower ethyleneamines (ie EDA, DETA, AEEA). hen. Instead, preferred ranges of turnover of 50 to 80% are set with respect to MEOA. Under these conditions, DEOA and TEOA are only partially converted, about 30% of the DEOA are converted into the value product AEEA. In addition, no increased proportion of morpholine, hydroxyethylpiperazine and hydroxy-ethlylmorpholin is formed, which could lead to difficulties in the distillative workup due to relatively low boiling points.

The reaction product of the process according to the invention contains ethylenediamine, diethylenetriamine, piperazine, triethylenetetramine, aminoethylethanolamine and higher cyclic and linear ethylene amines on amination products. In addition, unreacted MEOA, DEOA and TEOA are obtained.

The resulting reaction product of the second reaction stage preferably contains EDA and DETA in the weight ratio EDA: DETA = 4 to 16.

A typical reaction effluent with complete recycling of MEOA to the amination reactor (= to the second reaction stage) contains: 60-80 wt% EDA, 5-15 wt% DETA, 5-15 wt% AEEA, 5-15 Wt% piperazine (PIP), 4-7 wt% DEOA.

A typical reaction effluent, in the event that MEOA is not recycled to the amination reactor, additionally contains 25-50% by weight of MEOA and EDA, DETA, AEEA, PIP and DEOA in the proportions indicated above.

Depending on the conversion of MEOA in the amination reactor, there is a molar ratio MEOA: NH ₃ = 1: 8-1: 15 when MEOA is recycled to the amination stage.

The separation of the products is preferably carried out by distillation, being separated after increasing boiling point NH ₃ , H ₂ O, ethylenediamine, piperazine, monoethanolamine, diethylenetriamine, aminoethylethanolamine and DEOA.

Higher boiling products and unreacted TEOA are discharged as amine mix in the bottom of the DEOA separation. This mix is used as a basic asphalt additive and is largely characterized only by its amine number, so that a low proportion of TEOA according to the invention and other higher alcohols is advantageous.

Of the separated products, NH _{3 is} preferably reduced to the EO conversion (first reaction stage).

Unreacted MEOA can be recycled with the linear and cyclic ethylene amines and aminoethylethanolamine as co-product or the MEOA is recycled and thus the overall yield of the amination compared to the Alcohols increased. The recycling may optionally be done before the first (EO amination) or second (alcohol amination) reactor stage

In Appendix 2 is a scheme for a process variant according to the invention with MEOA feedback.

Examples

Example 1: Coupled production of ethylene amines and MEOA

EO (61.0 g / h) and NH ₃ (589 g / h) are transported analogously to EP-A-652 207 anhydrous continuously in the upflow mode in a tubular reactor (volume 75 ml, diameter 1 cm, length 1 10 cm) (catalyst ZSM-5 doped with 10% by weight lanthanum, analogous to EP-A-652 207, Catalyst A). Conditions: temperature 95 ⁰ C, pressure 140 bar, LHSV 10 h ^"1 .

After leaving the reactor, the mixture is admixed with hydrogen (1 g / h) and run in a second reactor (for example: volume 190 ml, length 1000 cm, diameter 1 cm). The amination is carried out on a Ni, Co, Cu catalyst on Al ₂ O ₃ (10 wt .-% CoO, 10 wt .-% NiO and 4 wt .-% CuO to Al ₂ O ₃ ) (LHSV -4, 5 h ^"1), at a pressure of 200 bar and a temperature in the range of 170-210 ⁰ C. the effluent of the reactor is released and the excess ammonia (approximately 550 g / h) under pressure (20 bar) was distilled off Afterwards, in a distillation cascade (see scheme Appendix 3), water and the various desired products are separated by distillation.

The following product mix is obtained:

EDA: 38 g / h; DETA: 6 g / h; Piperazine: 4 g / h; AEEA: 5 g / h;

DEOA: 3 g / h; MEOA 21 g / h

Example 2: Production of Ethylene Amines

In a second process variant, the MEOA (21 g / h) obtained in this otherwise analogous variant is completely recycled to the second reactor (amination reactor). The catalyst used in the EO reaction is a montmorillonite doped with 10% by weight of lanthanum (analogous to EP-A-652 207, Catalyst E).

In this case, after working up by distillation, a product mixture is obtained: EDA: 50 g / h DETA: 8 g / h AEEA: 7 g / h PIP: 6 g / h DEOA: 4 g / h

The bottom of the DEOA column is not further separated.

Claims

claims 1. A process for the preparation of ethylene amines, characterized in that in a first reaction stage ethylene oxide (EO) is continuously reacted with ammonia under water-free conditions on an inorganic ion exchanger as a heterogeneous catalyst, the resulting reaction product monoethanolamine (MEOA), diethanolamine (DEOA) and triethanolamine (TEOA) in the weight ratio MEOA: DEOA: TEOA = 80-94: 5.9-15: 0.1-5, and the reaction product is then continuously in a second reaction stage with ammonia in the presence of hydrogen and a heterogeneous Reacts hydrogenation catalyst. 2. A process for the preparation of ethylene amines according to claim 1, wherein the ethylene amines are ethylenediamine (EDA), diethylenetriamine (DETA), aminoethylethanolamine (AEEA), piperazine (PIP) and / or triethylenetetramine (TETA). 3. Process according to claims 1 or 2, characterized in that the inorganic ion exchanger is a phyllosilicate and / or framework silicate. 4. Method according to the preceding claim, characterized in that the phyllosilicate is a clay mineral. 5. Method according to the preceding claim, characterized in that the clay mineral is bentonite, montmorillonite and / or saponite. 6. The method according to claim 3, characterized in that the framework silicate is a zeolite. 7. The method according to any one of the preceding claims, characterized in that the inorganic ion exchanger is used in the form of a shaped catalyst body. 8. The method according to the preceding claim, characterized in that the proportion of inorganic ion exchanger in the shaped catalyst body is at least 5 wt .-%. 9. The method according to any one of the preceding claims, characterized in that the shaped catalyst body for pores having a diameter in the range of 2 nm 3 Fig. to 10 microns, a pore volume in the range of 0.1 to 1, 5 cm ³ / g, according to DIN 66134, having. 10. The method according to any one of claims 7 to 9, characterized in that the shaped catalyst body contains one or more metals in the oxidation state III, selected from scandium, yttrium and / or the lanthanides. 11. The method according to the preceding claim, characterized in that the weight fraction of the metals in the range of 0.5 to 50 wt .-% is. 12. The method according to claim 10, characterized in that the weight fraction of the metals in the range of 1 to 30 wt .-% is. 13. The method according to any one of the preceding claims, characterized in that no monoethanolamine (MEOA) is recycled to the second reaction stage. 14. The method according to any one of claims 1 to 12, characterized in that MEOA is recycled to the second reaction stage. 15. The method according to any one of the preceding claims, characterized in that the resulting reaction product of the second reaction stage in addition to MEOA EDA and DETA in the weight ratio EDA: DETA = 4-16. 16. The method according to any one of the preceding claims, characterized in that in the first reaction stage EO and ammonia in a molar ratio in the range of NH ₃ : EO = 15 - 30 is used. 17. The method according to any one of the preceding claims, characterized in that the reaction in the first reaction stage at a temperature in the range of 70 to 180 ⁰ C and an absolute pressure in the range of 50 to 150 bar. 18. The method according to any one of the preceding claims, characterized in that the reaction in the second reaction stage at a temperature in the range of 160 to 220 ⁰ C and an absolute pressure in the range of 150 to 250 bar. 19. The method according to any one of the preceding claims, characterized in that the heterogeneous hydrogenation catalyst in the second reaction stage one or more metals selected from Ni, Co, Cu, Ru, Re, Pd and / or Pt, on a support selected from Al ₂ O ₃ , TiO ₂ , ZrO ₂ and / or SiO ₂ . 20. The method according to any one of the preceding claims, characterized in that the reactions in the first and second reaction stage are each carried out in a tubular reactor with catalyst fixed bed.