EP1856025A1

EP1856025A1 - Method for producing a xylylenediamine

Info

Publication number: EP1856025A1
Application number: EP06708480A
Authority: EP
Inventors: Martin Ernst; Thilo Hahn; Johann-Peter Melder; Randolf Hugo; Kirsten Dahmen
Original assignee: BASF SE
Current assignee: BASF SE
Priority date: 2005-02-24
Filing date: 2006-02-23
Publication date: 2007-11-21
Also published as: JP2008531521A; DE102005008929A1; KR20070105382A; US20080154061A1; CN101128416A; WO2006089931A1

Abstract

The invention relates to a method for producing a xylylenediamine by the heterogeneously catalysed hydrogenation of a phthalodinitrile. According to the invention, said hydrogenation is carried out in the presence of a nickel skeleton catalyst, water, an alkali metal hydroxide and an ether, which acts as the solvent, at an absolute pressure ranging from 1 to 100 bar, a temperature of between 40 and 150 °C and without the addition of ammonia.

Description

Process for the preparation of a xylylenediamine

description

The present invention relates to a process for preparing a xylylenediamine by heterogeneously catalyzed hydrogenation of a phthalonitrile.

Xylylenediamine (bis (aminomethyl) benzene) is a useful starting material, e.g. for the synthesis of polyamides, epoxy hardeners or as an intermediate for the preparation of isocyanates.

The term "xylylenediamine" (XDA) includes the three isomers orffro-xylylenediamine, mete-xylylenediamine (MXDA) and para-xylylenediamine.

The term "phthalonitrile" (PDN) includes the three isomers of 1,2-dicyanobenzene = o-phthalodinitrile, 1,3-dicyanobenzene = isophthalodinitrile = IPDN and 1,4-dicyanobenzene = terephthalodinitrile.

The phthalonitriles are solids (for example, melts isophthalonitrile (IPN) at 161 ⁰ C) and have relatively poor solubilities in many organic solvents.

The two-stage synthesis of xylylenediamine by ammoxidation of xylene and subsequent hydrogenation of the obtained phthalonitrile is known in principle.

US-A-4,482,741 (UOP Inc.) describes the hydrogenation of PDN in the presence of ammonia, a supported Co / Ti catalyst and XDA as a solvent.

DE-A-21 64 169 (Mitsubishi Gas Chemical Co., Inc.) describes on page 6, last paragraph, the hydrogenation of IPDN to meta-XDA in the presence of a Ni and / or Co catalyst in ammonia as solvent.

JP-B-46008283 (Toray Industries Inc., ACS Abstract 75: 5222) relates to the hydrogenation of nitriles, such as aminocapronitrile, to primary amines in the presence of lead-containing nickel or cobalt catalysts.

US-B1-6,660,887 (Solutia Inc.) describes the preparation of 3-dimethylaminopropylamine (DMAPA) from N, N-dimethylaminopropionitrile (DMAPN) at low pressure in the presence of a nickel catalyst.

In particular, FR-A1-2 722 784 (Rhone Poulenc) teaches the hydrogenation of dinitriles, such as adiponitrile, to diamines in the presence of Ti-doped Raney nickel catalysts. No. 3,862,911 (and DE-A-2 260 978) (Rhone Poulenc) describes Ni / Cr / Fe / Al catalysts for the hydrogenation of nitriles, in particular adiponitrile. According to Example 6 B succeeds the hydrogenation of IPDN to MXDA in ethanol at 85 ° C and 40 bar with a yield of only 75%.

ACS Abstract No. 139: 381881 (JP-A2-2003 327563) (Mitsubishi Gas) discloses a process for the continuous hydrogenation of aromatic dinitriles in an ammonia-containing solvent, such as m-xylene, in a fixed bed irrigation liquid type reactor and in US Pat Presence of nickel or cobalt catalysts.

EP-A1-1 449 825 (Mitsubishi Gas Chem. Comp.) Describes a two-stage preparation of aromatic diamines from aromatic dinitriles, such as IPDN, in the presence of a Pd catalyst in the first stage and in the presence of a Ni or Co catalyst. sators in the second stage.

US 2,970,170 and GB-B-821 404 (California Research Corp.) relate to a multi-step production process for xylylenediamines starting from the corresponding phthalic acids. For dinitrile hydrogenation, eg in the presence of cobalt or nickel catalysts, pressures in the range of 1500 to 10,000 psig (103.4 to 689.5 bar), especially 2000 to 5000 psig (137.9 to 344.7 bar), and temperatures in the range of 180 to 400 ^° F (82 to 204 ^° C) (U.S. Pat., Col. 3, lines 65-71).

EP-A1-1 454 895 (Mitsubishi Gas Chem. Comp.) Describes a two-stage process for the hydrogenation of dicyanobenzenes at pressures of 5 to 300 bar, in particular 10 to 200 bar, in the presence of supported or unsupported Co, Ni, Pd , Ru- or Rh catalysts, preferably in the presence of ammonia and optionally in the presence of additives such as alkali metal hydroxides or alkaline earth metal hydroxides.

US-B1-6,476,267 (Sagami Chemical Research Center) relates to the preparation of aromatic primary amines from nitriles, such as IPDN, in the presence of supported Ni catalysts and polar solvents, preferably in the presence of NH ₃ , at pressures of 0.1 to 50 kg / cm ² G (0.1 to 49 bar), eg ≤ 19 kg / cm ² G (18.6 bar), and temperatures up to 200 ° C. Support material of the Ni catalyst is silica, alumina or activated carbon, preferably silica (all examples).

According to Example 22, the hydrogenation of IPDN in methanol in the presence of NH ₃ on a silica-supported Ni catalyst succeeds at 170 ° C and 15 kg / cm ² G (14.7 bar) in 79.5% yield.

GB-B-810 530 (PB Brindley et al.) Teaches the hydrogenation of iso- or terephthalodinitrile in the presence of ammonia, nickel or cobalt catalysts and aromatic Hydrocarbons, water, DMF, methanol or ethanol as a solvent. The pressure is up to 200 atm. (203 bar).

EP-A1-913 388 (Air Products) relates to the hydrogenation of nitriles, such as DMAPN, to amines in the presence of Raney cobalt catalysts, LiOH and water and in the absence of organic solvents, at pressures in the range of 1 to 300 bar, in particular 5 to 80 bar.

Disadvantages arise here due to the expense of feeding the educt nitrile into the reactor in the case of a solid, and in that the educt nitrile and / or intermediates, such as imines, form undesired by-products with the product amine to a high degree.

ACS Abstract No. 91: 91334 (JP-A2-54 041 804) (Takeda Chem. Ind.) Relates to the hydrogenation of nitriles, such as IPDN, in solvent mixtures of alcohols and cyclic see hydrocarbons on Raney Co or Raney Ni catalysts in eg 105-115 kg / cm ² (103-113 bar).

US-A-3,647,054 (ACS Abstract No. 73: 130762) (Japan Gas-Chemical Comp.) Describes the hydrogenation of phthalonitrile in liquid ammonia and in the presence of methanol on Raney Ni at 200 atm. (203 bar) and the subsequent purification of the crude product.

ACS Abstract No. 74: 31537 (JP-B4-45 03 0088) (Toray Ind.) Teaches the hydrogenation of aminocapronitrile in liquid ammonia on a modified Raney cocatalyst.

ACS Abstract No. 59: 61849 (JP 38 00 8719) (Toho Rayon Co.) relates to the hydrogenation of terephthalonitrile and isophthalonitrile in methanol on Raney Ni at 30 ^° C. in the presence of KOH.

US-A-3, 544,485 (Toyo Rayon) and ACS Abstract no. 73: 109473 (JP-B4-45 016 098) (Toray Ind.) Describe methods for activating Raney alloys.

DE-A1-100 65 031 (Degussa AG) relates to the use of Raney catalysts in the form of hollow bodies in hydrogenation processes.

The six German patent applications with the file references 10341615.3, 10341632.3, 10341614.5, 10341633.1, 10341612.9 and 10341613.7 (BASF AG) of 10.09.03 and the two German patent applications with the file numbers 102004042947.2 and 102004042954.5 (BASF AG) from 02/09/04 relate respectively for the production of XDA. German patent application with the file reference 102005003315.6 (BASF AG) of 24.01.05 describes a process for the preparation of a xylylenediamine by heterogeneously catalyzed hydrogenation of a phthalonitrile in the presence of a cobalt skeleton catalyst.

The present invention has for its object to find an improved economical process for the preparation of a xylylenediamine. The method should overcome one or more disadvantages of the prior art methods. The xylylenediamine, in particular MXDA, should thereby be obtained in high yield, in particular space-time yield, selectivity, purity and / or color quality.

[Space-time yields are given in 'product amount / (catalyst volume • time)' (kg / (l _K a _t • h)) and / or .product quantity / (reactor volume • time) '(kg / (l _Re a _k tor • h)].

Accordingly, a process for the preparation of a xylylenediamine by heterogeneously catalyzed hydrogenation of a phthalonitrile has been found, which is characterized in that the hydrogenation in the presence of a nickel skeletal catalyst, water, an alkali metal hydroxide and an ether as a solvent, at an absolute pressure in the range of 1 to 100 bar, at a temperature in the range of 40 to 150 ° C and without addition of ammonia is performed.

The process according to the invention is preferably used for the preparation of meta-xylylenediamine (MXDA) by hydrogenation of isophthalonitrile (IPDN).

Advantages of the method according to the invention include the, due to the driving without NH ₃ addition and low pressure driving, lower technical equipment and safety expenses and thus lower fixed costs (investment) and variable costs.

Furthermore, particularly small amounts of byproducts, such as higher than the xylylene diamine boiling products (at the same pressure) and amidines, for example of the formula I ₁ and their derivatives (dimers of MXDA of formula II) fall in the inventive selective process.

The PDN used in the process as starting material can be synthesized in a previous stage by ammoxidation of the corresponding xylene isomer. Such synthesis methods are e.g. in BASF patent applications EP-A-767 165,

EP-A-699 476, EP-A-222 249, DE-A-35 40 517 and DE-A-37 00 710, as well as in the above-mentioned. eight BASF patent applications for the production of XDA from 10.09.03 and 02.09.04 described.

The process according to the invention can be carried out as follows:

The starting material PDN is preferably used in a purity of> 90% by weight, in particular> 98% by weight, e.g. 98.2 to 99.9 wt .-%, used. Such purities may e.g. obtained by distillation or rectification of commercially available goods.

The hydrogenation process according to the invention is preferably used in the presence of from 0.5 to 15% by weight, especially from 2 to 10% by weight, very particularly from 2.5 to 7% by weight, in particular from 3 to 5% by weight, of water, each based on the used PDN performed.

For the hydrogenation of the phthalonitrile to the corresponding xylylenediamine (o-, m- or p-xylylenediamine) according to the equation

the PDN is dissolved and / or suspended in an ether. To increase the rate of dissolution and / or increase the amount of dissolved PDN, the dissolution process at elevated temperature, e.g. at 50 to 145 ° C, take place.

In the process according to the invention, preference is given to using from 15 to 75% by weight, in particular from 20 to 50% by weight, of solutions and / or suspensions of the PDN in the solvent or solvent mixture.

The solvent and / or suspending agent used is preferably a C _4-12 -dialkyl ether and / or C _3-12 -alicyclic ether, in particular a C _4-6 -dialkyl ether and / or C _4-6 -alicyclic ether. Examples of these are methyl tert-butyl ether (MTBE), diethyl ether (DEE), di-n-propyl ether, di-n-butyl ether, 1, 2-dimethoxyethane, 1,2-diethoxyethane, tetrahydrofuran (THF), 2 Methyl THF, tetrahydropyran, 1,3-dioxepane, 1,4-dioxane, 1,3-dioxane and 1,3-dioxolane. Particularly preferred is THF.

As solvent and / or suspending agent it is also possible to use a mixture of two or more of the solvents mentioned.

As catalyst for the hydrogenation, a nickel-skeletal catalyst is used according to the invention.

Typical examples of such catalysts are Raney ™ nickel catalysts. Here, the active catalyst as .Metallschwamm 'from a binary alloy of nickel and optionally other elements with z. As aluminum prepared by dissolving a partner with acid or alkali. Residues of the original alloying partner often act synergistically.

The catalysts used in the process according to the invention are preferably prepared starting from an alloy of nickel and a further alloying component which is soluble in alkalis. In this soluble alloy component, aluminum is preferably used, but other components such as zinc and silicon or mixtures of such components may be used.

To activate the catalyst, the soluble alloy component is wholly or partially extracted with alkali, for which example aqueous sodium hydroxide solution can be used. The catalyst can then z. B. be washed with water or organic solvents.

In the catalyst, one or more other elements may be present as promoters. Examples of promoters are metals of subgroups IB, VIB and / or VIII of the periodic table, such as chromium, iron, molybdenum, cobalt, copper, etc.

Activation of the catalysts by leaching the soluble component (typically aluminum) may be either in the reactor itself or prior to charging to the reactor. The preactivated catalysts are sensitive to air and pyrophoric and are therefore usually under a medium such. As water, an organic solvent or a substance that is present in the reaction according to the invention (solvent, starting material, product) stored and handled or embedded in an organic compound which is solid at room temperature. The catalysts can be used as powders for suspension hydrogenations, as granules or as shaped articles such as tablets or extrudates for fixed bed reactors.

Preferably, according to the invention, a nickel skeletal catalyst is used which is prepared from a Ni / Al alloy by leaching with aqueous alkali metal hydroxide solution, e.g. Sodium hydroxide solution, and subsequent washing with water was obtained, and preferably as promoters at least one of the elements Fe, Cr contains.

Such activated catalysts typically still contain nickel besides nickel

1 - 30 wt .-% Al, especially 2 - 20 wt .-% Al, especially 5 - 14 wt .-% Al, and

0-10 wt.% Cr, especially 0.1-7 wt.% Cr, very particularly 1-4 wt.% Cr, and / or 0-10 wt.% Fe, especially 0.1-7 % By weight of Fe, very particularly 1 to 4% by weight of Fe, the weight data in each case being based on the total weight of catalyst.

For example, a nickel skeleton catalyst A 4000 from Johnson Matthey can advantageously be used as the catalyst in the process according to the invention. This catalyst has the following composition:

Al: <14% by weight, Ni:> 80% by weight, Fe: 1 to 4% by weight, Cr: 1 to 4% by weight.

Preferably, the nickel skeletal catalyst employed does not contain lead (Pb) and / or cobalt (Co) and / or transition group IVB metal, i. no Ti, Zr and / or Hf.

The PDN is in the presence of alkali metal hydroxide (MOH), especially 0.001 to 5 mol% MOH, more preferably 0.002 to 1.5 mol% MOH, more preferably 0.005 to 1.2 mol% MOH, e.g. 1 mol%, MOH, in each case based on the PDN used reacted.

In a preferred embodiment, the appropriate amount of MOH is an aqueous solution, e.g. as 1 to 25 wt .-% aqueous solution used.

Possible alkali metals M are Li, Na, K, Rb and Cs. Preferably, M is K or Na. Particularly preferred is M = K.

It is also possible to use mixtures of two or more of the abovementioned alkali metal hydroxides (MOH), the amounts of MOH mentioned above then being based on the sum of the alkali metal hydroxides. For example, a NaOH-KOH mixture can be used. In a particular embodiment, the catalyst used is previously treated with an alkali metal hydroxide (M'OH) or a mixture of two or more alkali metal hydroxides M'OH, for example a mixture of NaOH and KOH. This treatment is particularly advantageous when the hydrogenation is carried out in the absence of MOH in the initial reaction mixture.

This treatment of the catalyst with M ¹ OH can be carried out by methods known to the person skilled in the art, for example by saturating the catalyst with M'OH, for example from 0.01 to 5.0% by weight of M'OH (based on the support material) Presence of a suitable solvent, eg water. (EP-A1-913388, US 6,429,338, US 3,636,108).

Possible alkali metals M 'are Li, Na, K, Rb and Cs. Preferably, M '= K or Na. Particularly preferred is M '= K.

The hydrogenation is carried out without the addition of ammonia.

The reaction temperature of the hydrogenation is in the range of 40 to 150 ⁰ C, preferably 50 to 120 ⁰ C, in particular 60 to 110 ° C, especially 70 and 105 ⁰ C _1, for example 80 to 100 ° C.

The absolute pressure in the hydrogenation is in the range from 1 to 100 bar, preferably from 2 to 80 bar, in particular from 5 to 60 bar, very particularly from 10 to 50 bar, e.g. 20 to 40 bar.

The hydrogenation is preferably carried out in a reaction stage. That Advantageously, several hydrogenation stages, e.g. taught in EP-A1-1 449 825 and EP-A1-1 454 895.

As reactors for the process according to the invention, for example, conventional high-pressure autoclave can be used.

For the hydrogenation, the reactors known to the person skilled in the art for this reaction (for example fixed-bed or suspension operation) as well as processes (continuous, semibatch, batch) can be used. In the suspension mode, a continuous process or semibatch process is preferred.

In the fixed catalyst bed mode, both the bottoms and the trickle run are possible. Preferred is a trickle way.

The hydrogenation reactor can be run in straight passage. Alternatively, a circulation mode of operation is possible in which a portion of the reactor output at the reactor gate input is returned, preferably without prior processing of the circulating current. Thus, an optimal dilution of the reaction solution can be achieved, which has a favorable effect on the selectivity. In particular, the circulation stream can be cooled by means of an external heat exchanger in a simple and cost-effective manner and thus the heat of reaction can be dissipated. As a result, the reactor can also be operated adiabatically, wherein the temperature rise of the reaction solution can be limited by the cooled circulation stream. Since the reactor does not have to be cooled even then, a simple and cost-effective design is possible. An alternative is a cooled tube bundle reactor.

In the preferred suspension procedure in the semibatch process, the nickel skeleton catalyst, the alkali metal hydroxide and water in the reactor are preferably initially charged and subsequently under the reaction conditions (pressure, temperature) the phthalonitrile in the solvent over a certain period of time (eg 2 to 8 hours). closed (semi-continuous driving).

In a particular embodiment, in particular of this procedure, the XDA corresponding to the PDN used is additionally presented with, for example, in amounts of 500-1500% by weight, based on the PDN to be used. In the case of the ortho-dinitrile, the XDA corresponding to the PDN used is the ortho-XDA, in the case of the meta-dinitrile the MXDA and in the case of the para-dinitrile the para-XDA.

The conversions of PDN achievable with the process according to the invention are in the range of> 95%, in particular> 99%, e.g. > 96 to 99.9% or 99.5 to 100%, with selectivities (for the formation of XDA) in the range of ≥ 80%, in particular> 85%, e.g. 86 to 99.5% or 90 to 99%.

The solvent-freed reaction product contains, in particular, ≦ 2% by weight, very particularly ≦ 1% by weight, e.g. 0 to 0.5% by weight, amidines of formula I and / or higher than the XDA boiling products, e.g. the corresponding (bisaminoalkyl) diarylamine II.

After carrying out the process according to the invention, the isolation of the XDA can be carried out, for example, by distillation or rectification. Examples

example 1

In a 300 ml high pressure autoclave with magnetically coupled gassing stirrer, sampling port, temperature control and an inlet for the continuous feed of educts, 60 g of THF, 1.19 g of water-wet, undoped Raney ™ nickel and 0.021 g of KOH in 1.73 g Water combined.

The autoclave was closed, the mixture made inert, and pressed to 10 bar Wasseroff. It was heated to 100 ^° C. under autogenous pressure and with stirring (500 rpm). Upon reaching this temperature was pressed to 36 bar of hydrogen and the stirrer speed to 1200 rev / min, increased. Subsequently, a solution of 7.2 g of IPDN in 83 g of THF was pumped in over 5 hours, while hydrogen was continuously fed (under pressure maintenance of 32-36 bar).

After 5 h, a sample was taken. GC analysis of the sample showed a conversion of 100% and a selectivity of 96.5%. No high boiling was observed. After completion of the dosing, the mixture was kept for a further 5 hours under the same conditions, but the selectivity did not decrease.

Example 2

Simulation of remixed driving:

In a 300 ml high pressure autoclave with magnetically coupled aeration stirrer, sampling port, temperature control and an inlet for the continuous feed of educts, 60 g MXDA, 5.95 g Raney ™ nickel A4000 Johnson Matthey, which had been previously washed with MXDA anhydrous , and 0.1 g of KOH in 0.5 g of water.

The autoclave was closed, the mixture made inert, and pressed to 10 bar hydrogen. It was heated to 100 ^° C. under autogenous pressure and with stirring (500 rpm). Upon reaching this temperature, hydrogen was injected to 36 bar and the stirrer speed was increased to 1200 rpm. Subsequently, a solution of 7.2 g of IPDN in 83 g of THF was pumped in over 1 h, while hydrogen was continuously fed (under pressure maintenance at 32-36 bar).

After 1 h, a sample was taken. GC analysis of the sample showed a MXDA content of 99.1% at 100% conversion. The content of high boilers was 0.24% (in GC-FI.%). After completion of the dosing, the mixture was kept for a further 2 hours under the same conditions, but the selectivity did not decrease.

Claims

claims

1. A process for preparing a xylylenediamine by heterogeneously catalyzed hydrogenation of a phthalodinitrile, characterized in that the hydrogenation in the presence of a nickel skeletal catalyst, of water, an alkali metal hydroxide and an ether as a solvent, at an absolute pressure in the range of 1 to 100 bar, at a temperature in the range of 40 to 150 ⁰ C and without addition of ammonia is performed.

2. The method according to claim 1 for the preparation of meta-xylylenediamine (MXDA) by hydrogenation of isophthalonitrile (IPND).

3. The method according to any one of the preceding claims, characterized in that the hydrogenation is carried out in a reaction stage.

4. The method according to any one of the preceding claims, characterized in that the hydrogenation is carried out at an absolute pressure in the range of 5 to 60 bar.

5. The method according to any one of the preceding claims, characterized in that the hydrogenation is carried out at a temperature in the range of 60 to 120 ⁰ C.

6. The method according to any one of the preceding claims, characterized in that the nickel-skeletal catalyst was obtained from a Ni / Al alloy by leaching with aqueous alkali metal hydroxide solution and washing.

7. The method according to any one of the preceding claims, characterized in that the nickel skeletal catalyst contains Fe and / or Cr as a promoter.

8. The method according to any one of the preceding claims, characterized in that the nickel-skeletal catalyst in addition to nickel still 1 - 30 wt .-% Al, and 0.1 - 10 wt .-% Cr and / or 0.1 - 10 Wt .-% Fe, in each case based on the total weight of catalyst.

9. The method according to any one of the preceding claims, characterized in that the hydrogenation in the presence of a C _4- i ₂ dialkyl ether and / or _C3-I2 - is performed alicyclic ether as solvent.

10. The method according to any one of the preceding claims, characterized in that the hydrogenation is carried out in the presence of tetrahydrofuran (THF) as a solvent.

11. The method according to any one of the preceding claims, characterized in that the hydrogenation is carried out in the presence of 0.001 to 5 mol% of alkali metal hydroxide based on the phthalonitrile used.

12. The method according to any one of the preceding claims, characterized in that one uses the alkali metal hydroxide as an aqueous solution.

13. The method according to any one of the preceding claims, characterized in that as alkali metal hydroxide potassium hydroxide (KOH) or sodium hydroxide

(NaOH).

14. The method according to any one of claims 1 to 12, characterized in that one uses as the alkali metal hydroxide, a mixture of sodium hydroxide and potassium hydroxide (NaOH and KOH).

15. The method according to any one of the preceding claims, characterized in that the heterogeneous catalyst used has been previously treated with an alkali metal hydroxide or a mixture of alkali metal hydroxides.

16. The method according to any one of the preceding claims, characterized in that the heterogeneous catalyst used previously with potassium hydroxide (KOH) was treated.

17. The method according to any one of the preceding claims, characterized in that a semi-batch driving and no batch driving is performed.

18. The method according to any one of claims 1 to 16, characterized in that a continuous driving and no semibatch or batch driving is performed.

19. The method according to any one of the preceding claims, characterized in that the hydrogenation in the presence of added xylylenediamine, which corresponds to the phthalodinitrile used, is carried out.

20. The method according to any one of the preceding claims, characterized in that the hydrogenation is carried out in the presence of 0.5 to 15 wt .-% water, based on the phthalonitrile used.