MXPA01002028A - Method for simultaneously producing a cyclic lactam and a cyclic amine - Google Patents

Abstract

The invention relates to a method for simultaneously producing a cyclic lactam and a cyclic amine by simultaneously reacting an aliphatic alpha, omega diamine and an aliphatic alpha, omega aminonitrile in the gas phase with water and in the presence of a heterogeneous catalyst.

Description

Procedure for the simultaneous obtaining of a cyclic lactam and a cyclic amine Description The present invention relates to a process for the simultaneous obtaining of a cyclic lactam and a cyclic amine by simultaneous reaction of an alpha, aliphatic diametric-diamine and an alpha, aliphatic aminonitrile orme in the gas phase with water, in the presence of a catalyst heterogeneous.

The obtaining of meczlas, which contain an aliphatic alpha, anmega-diamine and an aliphatic alpha, ormega-aminonitrile, by partial hydrogenation of an aliphatic alpha, oxime-dinitrile, for example, obtaining mixtures containing hexamethylenediamine and 6-aminocapronitrile by Partial hydrogenation of adipo-dinitrile is generally known. The further development of these mixtures for the generation of diamine and aminonitrile, is only achieved with a lot of technical work.

Cyclic lactams, such as caprolactam, are, as is known, intermediate products for obtaining important plastics, such as nylon. Cyclic amines are used in multiple fields as intermediates for the production of pharmaceutical and agricultural chemicals, corrosion inhibitors for non-ferrous metals, vulcanization accelerators and as auxiliary and sizing agents, antistatics and finishes, as well as resin crosslinkers.

From GB 1 358 862 (1974) it is known to obtain lactams from, especially, azacycloalkanes of five or more members or from diamines and water, in the presence of solid hydrogenation catalysts, at 150-400 ° C, in the liquid phase.

Agui is obtained, in the presence of Ra-Ni, Pt / C and Ru / Al2? 3, from piperidine / H20 / NH3 in the weight ratio of 1/10/9 (molar ratio of about 1/47/45). ) at 300 ° C (2-3 hours), pipe-ridona at a yield of around 50%. In comparison, it is formed from azepane ("hexamethyleneimine", HMI) / H20 / NH3 also in the weight ratio of 1/10/9 to 270 ° C, in the presence of Ra-Ni (5 hours), only 17.6% of the theoretical amount of caprolactam.

When hexamethylenediamine ("HMD") is used as diamine, then the yield in caprolactam is 10.7% even lower than the yield obtained from azepane, being, therefore, much lower than the technically necessary level, not forming, evidently , no azepane in this reaction.

Procedures for obtaining azabicycloalkanes from diamines, such as azepane from HMD, without the simultaneous obtaining of cyclic lactams are generally known.

This is how CA-A 920 606 describes the transformation of HMD, in the presence of H2 to HMD / H2 = 1: 2-70, at 150-250 ° C and 1-20 bar, in the presence of Co and Ni catalysts (type Raney, as well as on supports, such as Si02, AI2O3R giving azepane.

With incomplete yields (up to 44%), azepane selectivities of up to approx. 90% Secondary products are predominantly bis-hexamethylene-triamine and polyamines.

According to US Pat. No. 3,830,800, it is obtained from HMD in a solvent, such as dioxane, in the presence of RUO2 / C, also with low yields (<50%), good selectivities of azepane (91%).

DE-A 24 14 930 describes the condensation of HMD in the presence of metals of the group, comprising Ni, Co, Fe, Mn, Ag, Cu, Pd as active components, also on supports, such as AI2O3 or SiO2, in a high-boiling solvent, at temperatures of 200 ° C, with continuous, simultaneous distillation of the azepane formed (eg 139 ° C at normal pressure) from the reaction mixture. There are yields of up to 94%.

DE-A 25 32 871 refers to the continuous condensation of HMD in an inert solvent, in the presence of Ni or Co, also on supports of I2O3 or Si02, at temperatures of 80-150 ° C, eliminating the azepane continuously from the reaction mixture by azeotropic distillation with H20, to avoid the formation of oligo and polyamines.

From US-A 3,903,079 it is known, that in the condensation of HMD, using HMD / NH3 = 1: 15-30 (1:> 2) at 250-400 ° C, in the presence of zeolites loaded with 0.3-7% of metal cations of the group comprising Cu, Pd, Mn, Ni or Cr, in the gas phase, in the fixed bed or fluidized bed reactor, azepane can be obtained in yields of about 75%.

No. 470,900 discloses the condensation in the gas phase of diamines giving azacycloalkanes, including the HMD giving azepane, at 100-250 ° C, in the presence of Ni, Co, Fe or copper catalysts on supports, without the use of NH3.

Given a ratio of HMD / H2 of 1:20, a temperature of 150 ° C and a space velocity of 0.2, are reached in the presence of Ni / kieselgur, yields of azepane of 90%, in the presence of Cu / kieselgur is reached , given a HMD / H2 ratio of 1:20, a temperature of 150 ° C and a space velocity of 0.1, an azepane yield of 95%.

From EP-A 372 492 it is known to obtain azepane from HMD at 160-260 ° C in the presence of water vapor and hydrogen, in the presence of Pd / Al 2? 3, in the gas phase with a weight ratio between HMD and water from 20:80 to 99: 1. Here an azepane yield of 92% is achieved.

Processes for the reaction of cyclic amines, such as, for example, azepane, giving cyclic lactams, such as, for example, caprolactam, are also known.

According to Chem. Ber. 109 (1976) 3707-27 pyrrolidine can be transformed with oxygen under Pt catalysis with yields of 60% in pyrrolidone; on the contrary, for other cyclic amines the corresponding reaction results in a complex mixture of products.

The US-? No. 3,634,346 describes the reaction of a cyclic amine in the corresponding cyclic lactam by oxidation of a hydroperoxide in the presence of a metal ion catalyst. However, the best yields that can be achieved with this procedure (15.5% 2-pyrrolidone from pyrrolidine) are completely unsatisfactory for industrial processes.

The procedures for the oxidation of cyclic amines in the corresponding cyclic catheters with Hg- (II) compounds, as are known from US-A-3, 336, 299 and from Synth. Commun. 18 (1988) 1331-37, are completely unsatisfactory in terms of performance and problematic with respect to the further processing and removal of Hg-containing reaction residues.

The same applies to the oxidation of iodobenzene, as described in Tetrahedron Lett. 29 (1988) 6913-16.

Processes for obtaining cyclic lactams, for example caprolactam, from alpha, aliphatic αmega-aminoni, such as, for example, 6-aminocaproni-tryl, are also known.

US-A 2,357,484 describes the reaction of 6-aminocapronitrile at 200 to 350 ° C giving caprolactam in the presence of heterogeneous catalysts. Here, space-time yields of 0.02 to 0.03 g (product) / ml (catalyst) / h are achieved.

From EP-A 150 295 and US-A 4,628,085 the reaction of aminonitriles in cyclic lactams at 200 to 400 ° C is known in the presence of catalysts. The mixture of educts contains only up to 4% aminonitrile.

WO-A 96/22974 describes the reaction of 6-aminocapronitrile in caprolactam at 200 to 450 ° C, in the presence of catalysts, which in US-A 4,628,085 in the case of silicon dioxide are described as very short-lived.

From DE-A 19 632 006 it is known to convert 6-amincaproni-trilo into caprolactam at 220 to 380, in the presence of heterogeneous catalysts. The catalyst loads here amount to 0.1 to 1 g (educt) / ml (catalyst) / h.

The object of the present invention is to provide a process, which allows to simultaneously and technically and economically transform an aliphatic alpha, -mega-diamine and an aliphatic alpha, anmega-aminonitrile into a cyclic amine and a cyclic lactam.

Therefore, the procedure defined at the beginning was found.

Preferred starting materials in the process of the invention are alpha, aliphatic diametal diamines of the general formula (I) H2M- (CH2) n-NH2 (l) where n has the value 4, 5, 6 or 7, namely 1,4-diamino-butane, 1,5-diaminopentane, 1,6-diaminohexane ("hexamethylenediamine", "HMD") and 1, 7 -diaminoheptane, very preferably 1, 6-diaminohexane, or mixtures of such diamines (I).The diamines can carry one or more substituents on the carbon, such as alkyl groups having 1 to 6 carbon atoms, for example cyclopentyl, cyclohexyl, or cycloheptyl groups, or halogen groups. Preferably, the diamines are unsubstituted.

Such diamines and processes for their preparation are generally known.

As alpha, aliphatic α-metonymitriles are suitable in the process of the invention, firstly those corresponding to the general formula (II) H2N- (CH2) m-CN (N) wherein m has a value of 3, 4, 5, or 6, ie, 4-amino-butyronitrile, 5-aminovaleronitrile, 6-aminocapronitrile ("ACN") and 7-aminoenantonitrile, most preferably, 6-amino-amino capronitrile, or mixtures of such aminonitriles (II).

The aminonitriles can carry one or more substituents on the carbon, such as, for example, alkyl groups having 1 to 6 carbon atoms, cycloalkyl groups, such as cyclopentyl, cyclohexyl, or cycloheptyl, or halogen. Preferably, the aminonitriles will be unsubstituted.

Such aminonitriles and processes for their preparation are generally known and are commercially available.

Preferred mixtures of a diamine (I) and an aminonitrile (II) are those, in which n = m + 1. Those mixtures with a molar ratio between von aminonitrile (II) and diamine (I) are favorable from 5: 95 to 90:10, preferably from 10: 90 to 80:20, especially from 30: 70 to 60:40.

According to the invention, the reaction is carried out in the presence of a heterogeneous catalyst or mixtures of such catalysts.

As heterogeneous catalysts are appropriate, those, (a) that contain a dehydrogenating component (III) and (b) which contain an acid and / or amphoteric (IV) component.

As the dehydrogenating component (III), a metal of the group comprising Cu, Ag, Ni, Co, Rh, Ru, Ir, Os and Re, preferably from the group comprising Cu, Ag, Ni, Co, Rh and Ru, is suitable. especially, of the group comprising Cu, Co and Ru, or their mixtures.

Suitable as component (IV) are oxides, oxyhydrates, silicates, phosphates, heteropoly acids or acid zeolites of the metals Mg, Al, B, Ti, Zr, Hf, V, Nb, Ta, Mo, W, Fe, Cr, Ge , Zn, Sn, Bi, Th, U or of the lanthanides, such as La and Ce, preferably SIO2, gamma-Al203, oxides of Nb, Ta, Zr, as well as La, Nb, Zr, Al and B phosphates, or their mixtures, pu-diéndose, if desired, increase the acidity of these compounds by providing them with organic or, preferably, inorganic acids, such as phosphoric acid, sulfuric acid or hydrohalic acids.

The dehydrogenation component (III) can be used as a solid catalyst, for example, as Ni Raney or Co Raney or, preferably, as a support catalyst. Suitable support material is an inert material, for example, C, steatite or alpha-Al203, preferably an acid and / or amphoteric component, such as a component (III), especially SiO2, gamma-Al203, oxides of Nb, Ta, Zr, as well as La, Nb, Zr, Al and B phosphates, or their mixtures.

The quantitative relationships between the dehydrogenation component (III) and the component (IV) can be determined easily and without much work by the expert according to the desired reaction parameters, such as the ratio between the products or the catalytic activity, by means of some simple previous tests. Generally, weight ratios between component (III) and component (IV) are appropriate from 0.1: 99.9 to 50: 50, preferably from 0.5: 99.5 to 15: 85.

According to the invention, water is used in the process, preferably in a molar ratio to diamine (I) and aminonitrile (II) of more than 1, preferably in a molar ratio of water to diamine (I) and aminonitrile (II) from 3: 1 to 25: 1, especially from 5: 1 to 20: 1.

Advantageously, an inert gas, such as, for example, argon, CO or methane, can be added to the reaction mixture, preferably in a molar ratio between the inert gas and the diamine (I) and the aminonitrile (II) from 5: 1 to 100: 1, it being advantageous that the molar ratio between the inert gas and the diamine (I) and the aminonitrile (II) is so much smaller, the higher the molar ratio between water and diamine (I) and aminonitrile (II).

It is also advantageously possible to add hydrogen as an inert gas to the reaction mixture, which, according to the experiments made to date, increases the permanence of the heterogeneous catalyst, preferably by adding it in a molar ratio with respect to the diamine (I) from 0.01: 1 to 10: 1, especially, from 0.01: 1 to 5: 1. Increasing the molar ratio between hydrogen and diamine (I), especially in the case of highly hydrogenated components (III), especially Ni, Pt or Pd, the product ratio between the cyclic amine and the cyclic lactam can be displaced to the cyclic amine.

The process of the invention can be carried out at 200 to 600 ° C, preferably at 240 to 350 ° C, at pressures of 0.1 to 2 bar, preferably 0.75 to 1.5 bar, especially 0.9 to 1. , 1 bar, in a reactor suitable for this purpose, such as, for example, a fixed-bed reactor or in a fluidized-bed reactor.

Further processing of the product mixture can be carried out in a manner known per se, for example by extraction and / or, preferably, by distillation.

According to the invention, a cyclic lactam, preferably a cyclic lactam of the formulas (Va) or (Vb) is obtained in the process.

NH (Va) (CH2) n-l -CO- (CH2). NH (Vb) or a mixture of such lactams together with a cyclic amine, preferably a cyclic amine of the formulas (Via) or (VIb) ) (CH2) n NH (Via (VIb) (CH2) m + 1 NH or a mixture of such amines, representing n in the formulas (Va) and (Vía) an integer from 4 to 7 and m in the formulas (Vb) and (VIb) m an integer from 3 to 6.

Especially preferred lactams (Va) are those, in which n has a value of 4, 5, 6, and 7, especially, 6, and as lactams (Vb) those, in which m has a value of 3, 4, 5 and 6, namely, azolan-2-one ("2-pyrrolidone", "gamma-butyrolactone"). tama "), acixan-2-one (" piperidin-2-one "," valerolactam "), azepan-2-one (" caprolactam ") and azacyclooctan-2-one, most preferably, caprolactam, or mixtures of such lactams (Va) or (Vb).

Especially preferred amines (Via) are those, in which n has a value of 4, 5, 6 and 7, especially 6, and amines (VIb) especially preferred are those, in which m has a value of 3.4, 5 and 6, namely azolane ("pyrrolidine"), acixan ("piperidine"), azepane ("hexamethyleneimine", "HMI"), azacyclooctane, most preferably azepane, or mixtures of such amines (Via) or ( VIb).

When, preferably, starting compound with n m + 1 is used, then the lactams (Va) and (Vb) are advantageously identical, as are the amines (Via) and (VIb).

Furthermore, from the technical applications already mentioned, the amine (IV) obtained in the process of the invention can also be transformed into the corresponding lactam (V), preferably by recycling it in the process of the invention, especially in a mixture with the corresponding alpha, aliphatic diamine -membrane (I) and the corresponding alpha, aliphatic αmegaonitrile.

The reaction can be carried out, advantageously, under the reaction and process conditions mentioned for the process of the invention, in the presence of the aforementioned heterogeneous catalyst.

Example An aqueous solution, containing 50% by weight of a mixture from HMD and ACN in the molar ratio of 1.9: 1 was evaporated under addition of 10 1 of H2 / h (100 1/1 (catalyst) -h) with a charge of 100 g / 1 (catalyst) -h (equivalent to 50g of the sum from HMD and ACN per liter and hour) is passed in downflow to 275 ° C, on ml of Cu / Al2? 3 (macaroni 3 mm, length of the macaroni: 0.5 to 1.5 cm, inner diameter of the reactor: 29 mm).

The condensate discharge in refrigeration traps contains, according to gas chromatography analysis, with conversions of 91.2 HMD and 93.9% of ACN, caprolactam with a selectivity of 64.7%, with respect to the sum of the substances of departure, and azepano with a selectivity of 28.1%, with respect to the sum of the starting substances.

Claims (1)

1. PCIVIN I ACI? ES A process to co-produce a cyclic lactam and an a? > Cyclic inactivation by concomitant reaction of an aliphatic alpha, omega-diamma and an alpha, omega-aminonitrile aliphatic with water in gas phase, in the presence of a heterogeneous catalyst, using a molar ratio of water to the sum total of the alpha, omega- aliphatic diamine and alpha, omega, aliphatic aminonitrile within the range from 3 to 25, a molar ratio of alpha, aliphatic omega-aminonitrile to alpha, aliphatic omega-diamine within the range of 5:95 to 90:10 and a heterogeneous catalyst consisting of: a) a dehydrogenating component, and b) an acidic and / or amphoteric component. The process of claim 1, wherein the hexamethylenediamine and 6-aminocapronitrile are used as the aliphatic alpha, omega-diamine and the alpha, omega-aminonitrile aliphatic, respectively, to obtain ra? Epan as the cyclic amine and caprolactam as the lactam cyclic The process of claim 1 or 2, wherein the temperature is within the range from 200 to 6C0 ° C. The process of any of claims 1 to 3, in d _ /; _ '. < The dehydrogenating component in the heterogeneous catalyst is a metal selected from the group consisting of: Cu, Ag, Ni, Co, Pd, Pt, Rh, Pu, Ir, Os and Re. The process of any of claims 1 to 3, wherein the dehydrogenating component in the heterogeneous catalyst is a metal selected from the group consisting of: Cu, Co and Ru.