DE10336003A1 - Production of ethylene amine compounds used e.g. as intermediates for pharmaceuticals comprises continuous reaction of ethylenediamine in presence of heterogeneous catalyst in reaction column - Google Patents

Abstract

Production of ethylene amine compounds (I) comprises continuous reaction of ethylene diamine in the presence of a heterogeneous catalyst in a reaction column.

Description

The The present invention relates to a process for the preparation of Ethylene amines, especially diethylenetriamine (DETA), piperazine (PIP) and / or triethylenetetramine (TETA), by continuous reaction of ethylenediamine (EDA) in the presence of a heterogeneous catalyst.

ethyleneamines find use as solvent, Stabilizers, for the synthesis of chelating agents, synthetic resins, medicines, Inhibitors and surfactants Substances.

Especially Diethylenetriamine (bis (2-aminoethyl) amine; DETA) is used as a solvent for dyes and is starting material for the production of ion exchangers, Pesticides, Antioxidants, corrosion inhibitors, complexing agents, textile auxiliaries and absorbents for (acid) gases.

The ethylenediamine required as starting material (H ₂ N-CH ₂ -CH ₂ -NH ₂ ; EDA) can be prepared by known processes, for example by reacting monoethanolamine (MEOA) with ammonia.

to Preparation of ethylene amines such as DETA are numerous in the literature Method described.

In the prior art, ethylene amines such as DETA from monoethanolamine (MEOA) and ammonia are usually prepared in fixed bed reactors, wherein the catalysts contain as the active component, for example nickel, cobalt, copper or combinations thereof. Support material may be, for example, Al ₂ O ₃ , SiO ₂ or ZrO ₂ or combinations of these and other oxides. To maintain the catalyst activity, it is usually necessary to supply small amounts of hydrogen (eg about 0.1% by weight, based on the feed amount).

When The main product is EDA, the by-products are DETA, Piperazine (PIP) as well as higher Ethylene amines, i. Ethyleneamines with a boiling point higher than DETA (at the same pressure), and other compounds such as e.g. aminoethylethanolamine (AEEA).

There in particular DETA in addition to the main product EDA in larger quantities In the market, it is desirable to have the selectivity of DETA compared to that obtained in a single pass in the fixed bed reactor selectivity to increase. The selectivity of EDA and DETA can, within certain limits, by the molar ratio of ammonia controlled to MEOA. A high ammonia excess favors, especially at low MEOA turnover, the formation of EDA. At lower Excess ammonia and higher MEOA sales becomes the selectivity from DETA, but also the rest By-products increased.

It is possible, too EDA after concentration of the reaction in some cases in the To drive back the reactor about the DETA selectivity to increase. The formation of the rest By-products, especially AEEA, however, can not be avoided become.

In EP-A2-197 611 (Union Carbide Corp.) discloses a method of preparation of polyalkylenepolyamines by using two consecutively switched Reactors described.

in the The first reactor is the amination of MEOA with ammonia to transition metal catalysts (Ni, Re, carrier).

Of the Reactor discharge is over a second reactor, also containing a transition metal catalyst or loaded with a phosphate catalyst, sent.

To control the product distribution and increase the selectivity with respect to the linear ethylene amines, ethylene diamine, which originates from the work-up of the reaction effluent of the second reactor and also contains MEOA and H ₂ O, is fed in before the second reactor.

disadvantage This method is that AEEA is preferred to piperazine and not reacted to DETA and by reacting EDA with MEOA additional Amounts of AEEA are formed.

The synthesis of DETA can also be carried out by the reaction of EDA in a fixed bed reactor by known processes, the main by-product being PIP (cf., for example, US Pat US 5,410,086 (Burgess), GB-A-1,508,460 (BASF AG) and WOA1-03 / 010125 (Akzo Nobel)).

at a turnover of e.g. about 30% can have a DETA selectivity of about 70% can be achieved. When using pure EDA as starting material no AEEA as a by-product. The formation of higher ethyleneamines is by the partial sales procedure largely avoided.

Due to the unfavorable position of the chemical equilibria, however, more PIP would be formed at higher conversion. Because of the formation of ammonia in the conversion of EDA to DETA (2 EDA → DETA + NH ₃ ), the higher the conversion, the greater is the recovery of DETA with ammonia to EDA.

The Partial sales driving leads to high circulating currents at EDA (repatriation) and thus to an increased Energy consumption, especially in the EDA cleaning column.

A parallel BASF patent application with the same filing date concerns a process for producing ethylene amines by reaction of monoethanolamine (MEOA) with ammonia in the presence of a catalyst in a reactor (1) and separation of the resulting reaction effluent, wherein in the separation obtained ethylenediamine (EDA) in a separate reactor (2) in the presence of a catalyst to diethylenetriamine Implemented (DETA) and the resulting reaction product of the separation the resulting from reactor 1 Reaktionsaustrags is supplied.

to Addition of alcohols to olefins to corresponding ethers [e.g. MTBE (methyl tertiary butyl ether) and TAME (Tertiary Amyl Methyl Ether)] are known in the literature method, which in a reaction column carried out become. The method also referred to as reactive distillation are e.g. in the textbook 'Reactive Distillation', edited by K. Sundmacher and A. Kienle, Publisher Wiley-VCH (2003), in detail described.

applications of reactive distillation are also in the areas of esterification, Saponification and transesterification, production and saponification of acetals, Production of alcoholates, aldol condensations, alkylations, Hydrolysis of epoxides, hydration of olefins, isomerizations and hydrogenations.

Of the Present invention was based on the object, an improved economical process for the selective production of ethylene amines, including in particular diethylenetriamine (DETA), in high space-time yield (RZA).

Accordingly, became a process for the production of ethylene amines by continuous Reaction of ethylene diamine (EDA) in the presence of a heterogeneous catalyst found, which is characterized in that the reaction in performs a reaction column.

at The ethylene amines are in particular diethylenetriamine (DETA), piperazine (PIP) and / or triethylenetetramine (TETA).

The conversion then proceeds according to the following equations, for example: 2 EDA → DETA + NH ₃ 2 EDA → PIP + 2 NH ₃ 3 EDA → TETA + 2 NH ₃ DETA + EDA → TETA + NH ₃

According to the invention was recognized that the disadvantages of the methods of the prior art be avoided, if one the synthesis of Ethylenaminen, in particular DETA, by continuous reaction of EDA in a reaction column (reactive distillation). By the continuous removal of DETA and / or TETA from the column below the reaction zone (above Swamp and / or over a side print) Follow-up reactions are largely suppressed and thereby becomes a driving style with high turnover and even full turnover of EDA allows.

By the continuous removal of ammonia from the column (preferred at the top of the column, also as a mixture with lighter than DETA boiling Components) becomes the reverse reaction from DETA to EDA largely inhibited and so the formation of DETA accelerated. The reaction can therefore be at other pressures, advantageously lower pressures, carried out than when using a conventional fixed bed reactor (tubular reactor with fixed catalyst bed) optimum pressure range.

Of the Absolute pressure in the column is preferably 1 to 20 bar, in particular 5 to 10 bar.

The Temperature in the region of the column in which the reaction of EDA to ethylene amines takes place (reaction zone) is generally 100 up to 200 ° C, in particular 140 to 160 ° C.

The Number of theoretical plates in the column is preferred a total of 20 to 100.

The Number of theoretical plates in the reaction zone is preferred 5 to 30, especially 10 to 20.

The Number of theoretical plates in the rectifying section above the reaction zone is preferred 5 to 30, especially 5 to 15.

The Number of theoretical plates in the stripping section below the Reaction zone is preferably 5 to 40, in particular 10 to 20.

The Addition of EDA to the column can be carried out below the reaction zone liquid Shape or gaseous respectively.

The Addition of EDA to the column can also be carried out in liquid form above the reaction zone.

in the inventive method Both pure EDA, e.g. in a purity> 98 wt .-%, in particular> 99 wt .-%, as well EDA, which contains piperazine (PIP), e.g. > 0 to 25 wt .-% PIP, and / or others Contains ethyleneamines, be fed to the column.

It may also be after partial or complete separation of ammonia and water obtained EDA crude product from a reaction of MEOA be used with ammonia.

The Reaction is particularly preferred in the presence of hydrogen, especially in the presence of 0.01 to 1 wt .-% hydrogen on the feed amount of EDA performed.

The Addition of hydrogen into the column is preferably carried out below the reaction zone.

One Mixture of ammonia, other components with a boiling point lower as DETA (at the same pressure) (low boilers) and optionally hydrogen is preferred over Head of the column taken.

The over head The mixture taken from the column can also be aliquots of unreacted EDA contain.

The over head taken mixture can also partially condensed while ammonia and optionally hydrogen predominantly removed in gaseous form (separated) and the liquefied Share as return given to the column.

The weight ratio the return amount of Column (column return quantity) to the amount of the feed to the column is preferably 0.5 to 10, in particular 0.5 to 2.

One Mixture of DETA, piperazine (PIP), TETA and other components higher with a boiling point as DETA (at equal pressure) (high boilers) is preferred over bottoms taken from the column.

The over swamp The mixture taken from the column can also be aliquots of unreacted EDA or the total amount of unreacted EDA.

In a special process design is the column below the reaction zone divided by a side take.

On the Side draw are preferably unreacted EDA, PIP or mixtures taken from it.

That over the Product withdrawn from the side trigger can also contain DETA.

That over the Slip-on product is taken in liquid or gaseous form.

In the reaction zone is preferably a catalyst as catalyst containing Ni, Co, Cu, Ru, Re, Rh, Pd and / or Pt or a shape-selective Zeolithkatalystor or a phosphate catalyst used.

The one or more metals of the transition metal catalyst are preferably applied to an oxidic support (eg Al ₂ O ₃ , TiO ₂ , ZrO ₂ , SiO ₂ ).

The Heterogeneous catalysts can in the form of solid catalyst beds within the column or in separate containers outside be accommodated in the column. They can also be called bulkings, e.g. as a bed in a distillation pack, used, molded into packing or shaped articles are pressed, for example, to Raschig rings, in filter fabric introduced and formed into rolls (so-called Bales) or column packs be applied to distillation packs (coating) or as a suspension in the column, in this case preferably as a suspension on column bottoms, be used.

In Method with heterogeneously catalyzed reactive distillation can Advantageously, the "bales" technology developed by the company CDTech can be used.

Further Technologies are packed or packed with special floor constructions suspended catalysts.

Multichannel packings or cross-channel packages (see, e.g., WO-A-03/047747) easy filling and discharging catalysts which are in particulate form (e.g. Bullets, stringers, Tablets), with little mechanical stress on the catalyst.

An important point in reactive distillation is the provision of the residence time required for the course of the reaction. It is necessary to increase the residence time of the liquid in the column in a targeted manner compared to a non-reactive distillation. It uses special constructions of column internals, such as tray columns with bubble cap trays and a greatly increased level, high residence times in the downcomers of tray columns or separately arranged external dwell time. It is also possible to provide external containers for providing the reaction volume. Anstaupackungen offer the Possibility to increase the residence time of the liquid by about a factor of 3 compared to packed and packed columns.

The Design of the reaction column (e.g., number of separation stages in the Column sections reinforcement part, Stripping section and reaction zone, reflux ratio, etc.) can by the Professional familiar to him Methods are made.

Reaction columns are described in the literature, for example in:
'Reactive distiullation of non-ideal multicomponent mixtures', U. Hoffmann, K. Sundmacher, March 1994, Trondheim / Norway,
'Reactive Distillation Processes', J. Stichlmair, T. Frey, Chem. Ing. Tech. 70 (1998) 12, pages 1507-1516,
'Thermodynamic Principles of Reactive Distillation', T. Frey, J. Stichlmair, Chem. Ing. Tech. 70 (1998) 11, pages 1373-1381,
WO-A-97/16243 of 9.5.97,
DD patent 100701 of 5.10.73,
US 4,267,396 of May 12, 1981,
, Reactions in distillation columns', G. Kaibel, H.-H. Mayer, B. Seid, Chem. Ing. Tech. 50 (1978) 8, pages 586-592, and literature cited therein,
DE-C2-27 14 590 dated 16.8.84,
EP-B-40724 of 25.5.83,
EP-B-40723 of 6.7.83,
DE-C1-37 01 268 of 14.4.88,
DE-C1-34 13 212 of 12.9.85,
'Production of potassium tert-butoxide by azeotropic reaction distillation', Wang Huachun, Petrochem. Closely. 26 (1997) 11,
'Design aspects for reactive distillation', J. Fair, Chem. Eng. 10 (1998), pages 158-162,
EP-B1-461 855 dated 09.08.95,
'Consider reactive distillation', J. DeGarmo, V. Parulekar, V. Pinjala, Chem. Eng. Prog. 3 (1992),
EP-B1-402 019 of 28.6.95,
'La distillation réactive', P. Mikitenko, Pétrole et Techniques 329 (1986), pages 34-38,
Geometry and efficiency of reactive distillation bale packing, H. Subawalla, J. Gonzalez, A. Seibert, J. Fair, Ind. Eng. Chem. Res. 36 (1997), pages 3821-3832,
'La distillation réactive', D. Cieutat, Pétrole et Techniques 350 (1989),
'Preparation of tert-amyl alcohol in a reactive distillation column', J. González, H. Subawalla, J. Fair, Ind. Eng. Chem. Res. 36 (1997), pages 3845-3853,
, More uses for catalytic distillation, G. Podrebarac, G. Rempel, Chem. Tech. 5 (1997), pages 37-45,
'Advances in process technology through catalytic distillation', G. Gildert, K. Rock, T. McGuirk, CDTech, pages 103-113,
WO-A-03/047747 from 12.06.03, and
WO-A1-97 / 35,834th

The Working up of the product streams occurring in the process according to the invention, the especially the most desired DETA, but also triethylenetriamine (TETA), PIP and unreacted EDA can, according to the skilled person known distillation respectively. (See, e.g., PEP Report No. 138, "Alkyl Amines", SRI International, 03/1981, pages 81-99, 117).

The for the pure distillation of the individual products, above all the most desired DETAs needed Distillation columns can by the expert familiar with him Methods (e.g., number of plates, reflux ratio, etc.).

The Driving with a side take-off in the stripping section below the reaction zone the reaction column offers particular advantages in the further work-up for the pure recovery of the individual products.

Of the Side take-off current, consisting predominantly from PIP, unreacted EDA or mixtures thereof contains only small ones Quantities of DETA and high boilers, especially in the case of gaseous removal of the side take-off flow. He can therefore in the workup, separated from the bottom draw stream of the reaction column, are fed directly to the site, where the cleaning of EDA and PIP is performed, instead of the first Separation of the low-boiling components of DETA and high-boiling compounds to go through.

subsets of the side stream also be recycled to the reaction column itself. This is special advantageous if the side stream predominantly EDA and little or contains no PIP.

Of the Bottom take-off stream of the reaction column contains less in this procedure Low boilers (EDA and PIP), so that the column to separate the low-boiling components of DETA and high boilers relieved becomes.

If the reactive distillation is carried out at low pressures, For example, 1 to 3 bar, it is also possible, the bottom draw stream obtained at bottom temperatures of about 200 to 240 ° C free of EDA and PIP. The bottom draw stream can then optionally in the workup to supplied to the site where the cleaning of DETA is performed, rather than the first Separation of the low-boiling components of DETA and high boilers run through.

example 1

1 in Appendix 1 shows an embodiment the process according to the invention in which pure EDA or an EDA / PIP mixture is fed together with hydrogen to the reaction column continuously below the catalytic packing and a mixture comprising DETA, unreacted EDA, PIP, TETA and high boilers (SS, ie components with a boiling point higher than DETA) is obtained via sump. Ammonia, hydrogen and low boilers (LS, ie components with a boiling point lower than DETA) are separated overhead.

Example 2

2 in Appendix 2 shows an embodiment of the inventive method in which pure EDA or an EDA / PIP mixture together with hydrogen of the reaction column is fed continuously below the catalytic packing and a mixture containing DETA, TETA and high boilers (SS, ie components with a boiling point higher as DETA) over swamp. Ammonia, hydrogen and low boilers (LS, ie components with a boiling point lower than DETA) are separated overhead.

In a side take in the stripping section below the reaction zone of Reaction column is separated PIP, optionally as a mixture with EDA.

Claims (31)

Process for the preparation of ethyleneamines by continuous reaction of ethylenediamine (EDA) in the presence of a heterogeneous catalyst, characterized in that the reaction is carried out in a reaction column. Process for the preparation of ethylene amines according to Claim 1, wherein the ethyleneamines are diethylenetriamine (DETA), piperazine (PIP) and / or triethylenetetramine (TETA). Process according to claims 1 or 2, characterized that the absolute pressure in the column is 1 to 20 bar. Method according to one of the preceding claims, characterized characterized in that the temperature in the region of the column, in which the conversion of EDA to ethylene amines takes place (reaction zone), 100 to 200 ° C is. Method according to one of the preceding claims, characterized characterized in that the number of theoretical plates in the Total column is 20 to 100. Method according to one of the preceding claims, characterized characterized in that the number of theoretical plates in the Reaction zone is 5 to 30. Method according to one of the preceding claims, characterized in that the number of theoretical plates in the rectifying section is above the reaction zone is 5 to 30. Method according to one of the preceding claims, characterized characterized in that the number of theoretical plates in the stripping section below the reaction zone is 5 to 40. Method according to one of the preceding claims, characterized characterized in that in the reaction zone as catalyst a catalyst containing Ni, Co, Cu, Ru, Re, Rh, Pd and / or Pt or a shape-selective Zeolithkatalystor or a phosphate catalyst is used. Method according to one of the preceding claims, characterized characterized in that the catalyst is introduced as a bed in a distillation packing is. Method according to one of claims 1 to 9, characterized that the catalyst as a coating on a distillation pack is present. Method according to one of claims 1 to 9, characterized that the catalyst is located in an outside of the column dwell is present. Method according to one of the preceding claims, characterized characterized in that the addition of EDA to the column in liquid form takes place below the reaction zone. Method according to one of claims 1 to 12, characterized that the addition of EDA into the column is gaseous below the reaction zone he follows. Method according to one of claims 1 to 12, characterized that the addition of EDA to the column in liquid form above the reaction zone he follows. Method according to one of the preceding claims, characterized in that the EDA is fed to the column in a purity of> 98% by weight. Method according to one of claims 1 to 15, characterized that fed to the column EDA, piperazine (PIP) and / or other ethyleneamines. Method according to one of the preceding claims, characterized in that the Um in the presence of hydrogen. Method according to the preceding claim, characterized characterized in that the reaction in the presence of 0.01 to 1 wt .-% Hydrogen based on the feed amount of EDA is performed. Method according to one of the two preceding claims, characterized characterized in that the addition of hydrogen to the column below the Reaction zone occurs. Method according to one of the preceding claims, characterized marked that over Head of the column a mixture of ammonia, other components with a boiling point lower than DETA (low boilers) and optionally Hydrogen is removed. Method according to the preceding claim, characterized marked that over Top of the column taken mixture also subsets of unreacted Contains EDA. Method according to one of the two preceding claims, characterized marked that over Head removed mixture is partially condensed while ammonia and optionally hydrogen predominantly gaseous be removed and the liquefied Share as return is given to the column. Method according to one of the preceding claims, characterized in that the weight ratio of the return amount of the column to the amount of the feed to the column is 0.5 to 10. Method according to one of the preceding claims, characterized characterized in that over swamp the column is a mixture of DETA, piperazine (PIP), TETA and others Components with a boiling point higher than DETA (high boilers) taken becomes. Method according to the preceding claim, characterized marked that over marsh taken from the column mixture and aliquots of unreacted Containing EDA or the total amount of unreacted EDA. Method according to one of the preceding claims, characterized characterized in that the column below the reaction zone a side print is divided. Method according to the preceding claim, characterized marked that over taken from the side take unreacted EDA, PIP or mixtures thereof become. Method according to one of the two preceding claims, characterized marked that over the product taken from the side draw contains DETA. Method according to one of the three preceding claims, characterized characterized in that over the Side suit accumulating product is removed in liquid form. Method according to one of claims 27 to 29, characterized that over the side suit accumulating product is removed in gaseous form.