The method of producing caprolactam

 

(57) Abstract:

Caprolactam is produced by interaction of a solution of the nitrile 6-aminocaproic acid with water in the liquid phase at elevated temperature. The reaction mass without adding catalyst is heated in the reactor And the mixture I consisting mainly of water, caprolactam, and high-boiling fractions. From a mix I remove the water and get the mixture II, consisting mainly of caprolactam and high-boiling fractions. Mixture II distillation divided into caprolactam and high-boiling fraction. Further provides for processing of high-boiling fractions in three variants: high-boiling fraction is returned to the reactor And process in the second reactor B, the high-boiling fraction under reduced pressure in the presence of a base process in the reactor C. And the reaction mixture from reactor B and is subjected to distillation to obtain an additional amount of caprolactam in the same pattern as for the reaction mass from the reactor A. the Process in the reactor And carried out at 200 - 370oC, a pressure of 0.1 - 50 MPA when the excess water 10 to 150 moles per 1 mole of the nitrile. This results in a simpler technology due to the absence of phase separation and regeneration of the catalyst. Due to the high ceased method of obtaining caprolactam by reacting the nitrile 6-aminocaproic acid with water at elevated temperature.

In U.S. patent 4628085 describes the interaction of nitrile 6 - aminocaproic acid with water in the gas phase at the specific acidic silica gel (PorasilA) at 300oC. When diluted with water, ammonia and a mixture of hydrogen and nitrogen can be obtained caprolactam with quantitative yield and selectivity higher than 95%. However, already for 150 hours in the decontamination decrease output by at least 5% and a selectivity of at least 5%.

Such gas-phase method is described also in U.S. patent 4625023. There miss vysokorazvetvlennyi gas stream nitrile 6-aminocaproic acid, adipodinitrile, ammonia, water and carrier gas through a layer of silica gel and of a catalyst containing copper, chromium, barium and titanium oxide. Selectivity to caprolactam is 91% at exit 85%.

Both methods have the disadvantage that the applied heterogeneous catalyst abruptly deactivated. In addition, you must vysokorazvetvlennyi gas stream nitrile 6 - aminocaproic acid with water to apply for the reaction to these heterogeneous catalysts. This causes the high cost of energy costs for evaporation and a large volume of the reactor.

In U.S. patent 2245129 described getting lean is for 20 hours. The formation of caprolactam were not observed.

So was the technical problem of developing a method of producing caprolactam using nitrile 6-aminocaproic acid, carried out with high selectivity in the liquid phase and without catalyst, in particular, should be minimized content of by-products.

In line with this, a method was found of obtaining caprolactam by reacting the nitrile 6-aminocaproic acid with water at elevated temperature, in which

(a) an aqueous solution of nitrile 6-aminocaproic acid in the liquid phase without the addition of catalyst is heated in the reactor And the mixture I consisting mainly of water, caprolactam, and high-boiling fractions, then

(b) water from a mixture of I are removed from the mixture II, consisting mainly of caprolactam and high-boiling fractions, then

(C) from a mixture of II by distillation separately produce caprolactam and high-boiling fraction, and then

(G1) the high-boiling fraction from step (C) is served in the reactor And on the stage (a), or

(G2) high-boiling fraction is similar stage (a) is heated in the second reactor B and then treated similarly to the stages (b) and (C) obtaining Austlii base is heated in a reactor and leaving the reaction mixture is subjected to distillation to obtain caprolactam.

Used according to the invention as starting substances nitrile 6-aminocaproic acid usually get the hydrogenation of adipodinitrile by well-known methods, for example, described in patent applications FRG DE-A 836938, DE-A 848654 or in U.S. patent 5151543.

You can also submit to the reactor And the mixture, which may contain, in General, the nitrile 6-aminocaproic acid, and hexamethylenediamine were, adipodinitrile and/or caprolactam, and high-boiling fractions, which are formed during the processing of obtained according to the invention caprolactam.

Further, preferably, water is supplied in excess, particularly preferably used per 1 mol of the nitrile 6-aminocaproic acid from 10 to 150, in particular from 20 to 100 mol of water to obtain an aqueous solution of nitrile 6-aminocaproic acid. In another preferred embodiment, the invention is applied is usually from 5 to 25 moles of water per 1 mol of 6-aminocaproic acid and possible solution, generally speaking, the addition of organic solvent to dilute further to the concentration of nitrile 6-aminocaproic acid from 5 to 25 wt.%.

As a suitable solvent, for example, to specify:

alcohols with 1-4 carbon atoms, such as m the e l e C tetraethylene glycol, ethers, such as tert.butyl ether, dietilenglikoluretan ether, alkanes with 6-10 carbon atoms, such as N. hexane, N. heptane, N. octane, called Noonan, N. Dean, and cyclohexane, benzene, toluene, xylene, lactams, such as pyrrolidone, caprolactam, or N-alkyl-lactam with 1-4 carbon atoms in the alkyl part, such as N - organic N-methylcaprolactam or N-ethylcaproic.

In another embodiment, in the reaction mixture can be added from 0 to 5, preferably from 0.1 to 2 wt.% ammonia, hydrogen or nitrogen.

According to the invention the reaction in stage (a) is conducted at temperatures in the range from 200 to 370, preferably from 220 to 350oC, particularly preferably from 240 to 320oC.

Usually the reaction in stage (a) are under pressure, and a pressure typically in the range from 0.1 to 50, preferably from 5 to 25 MPa, is chosen so that the reaction mixture was kept in the liquid phase.

The reaction time in the reactor And depends essentially on the chosen parameters of the method and is in continuous process, generally speaking, from 20 to 180, preferably from 20 to 90 minutes. At shorter reaction times, typically the military at the present time observations.

The cyclization of (stage (a)) are preferably continuously in the reactor And, mainly in the tubular reactor, in the tank with agitator or a combination of these devices.

The cyclization of (stage (a)) can be performed periodically. The reaction time is usually from 30 to 180 minutes.

From the reactor according to the invention leaves the mixture I containing, essentially, from 50 to 98, preferably from 80 to 95 wt.% water and from 2 to 50, preferably from 5 to 20 wt.% mixture consisting essentially of from 50 to 90, preferably from 65 to 85 wt.% caprolactam and from 10 to 50, preferably from 15 to 35 wt.% the high-boiling fraction.

At the stage (b) according to the invention are removed in a mixture of water I in the usual manner, preferably by distillation, to obtain a mixture of II, consisting essentially of caprolactam and high-boiling fractions. In a preferred embodiment of the invention are distillation under reduced pressure in the range from 10 to 500 mbar, preferably from 50 to 350 mbar, and the applied vacuum distillation column contains from 2 to 20, preferably from 4 to 10 theoretical plates.

At the stage (b) according to the invention is achieved by distillation obtained in stage (b) mixture II is Ino distillation stage (C) carried out under pressure in the range from 0.1 to 100 mbar, preferably from 1 to 20 mbar. In the calculation of the applicable amount of nitrile 6 - aminocaproic acid is observed yield of caprolactam during the distillation in the range from 50 to 90, preferably from 65 to 85 wt.%.

Obtained in stage (C) high-boiling fraction according to the invention can be processed in various ways, with or

on stage (G1) high-boiling fraction from step (C) is served in the reactor And on the stage (a), or

on stage (G2) high-boiling fraction is similar stage (a) is heated in another reactor B and then treated similarly to the stages (b) and (C) additional amounts of caprolactam, preferably high-boiling fraction is mixed with from 5 to 25, preferably from 10 to 15-fold weight excess amount of water and then at a temperature in the range from 250 to 350, mostly from 280 to 320oC, is heated in the reactor B in the period from 30 to 120, mainly from 45 to 90 minutes, or

on stage (G3) high-boiling fraction under reduced pressure, in General, in the range from 1 to 50, mainly from 1 to 10 mbar, in the presence of a base, usually from 1 to 10, mostly from 1 to 3 wt.%, heated in a reactor, preferably a tubular reactor, at a temperature of the sustained fashion by distillation, mainly under pressure in the range from 1 to 50, preferably from 1 to 10 mbar, with additional amounts of caprolactam. In a preferred embodiment of the invention applied to the distillation column with the number of theoretical plates in the region from 2 to 20, particularly preferably from 5 to 10.

As the base used is preferably a hydroxide of alkali metals such as sodium hydroxide and potassium hydroxide or a mixture thereof.

The advantage of the method according to the invention lies in the fact that they get caprolactam with high selectivity and high yield, based on the nitrile 6-aminocaproic acid, in the liquid phase without catalyst and with a short reaction time.

Examples

Example 1

In the tubular reactor was heated to 10 wt.%-s ' solution of 6 - aminocaproate (DCA) in water up to 300oC, and the average processing time was 1 hour. In facing the reaction mixture DCA was not detected. The mixture of products (mixture I) contained 90 wt.% water and 10 wt.% a mixture consisting of 76 wt.% caprolactam and 24 wt.% the high-boiling fraction. The mixture was then I was subjected to distillation under a pressure in the range from 100 to 300 mbar in the column for vacuum distillation with five her (mixture II) caprolactam and high-boiling fraction. Mixture II in the second column for vacuum distillation (pressure in the range from 3 to 10 mbar) were divided by the fraction of caprolactam (parent product) and high-boiling fraction (CBM product). Obtained the yield of caprolactam was 74 wt.%, since during the processing of an additional 2 weight. % obtained as described above, caprolactam turned into a high-boiling fraction (essentially oligomeric lactam).

Example 2

The high-boiling fraction obtained in example 1, was mixed with 10-fold weight excess of water and heated at 300oC in a separate reactor for 1 hour. The resulting mixture of products was processed as described in example 1, and received 74 wt.% caprolactam, so that the total yield of caprolactam, based on the initial number of DCA, amounted to 93 wt.%.

Example 3

Repeated example 1 and then the high-boiling fraction is returned to the cyclization reactor (reactor A). Then reprocessed in the same manner as in example 1, and the total yield of caprolactam was 93 wt.%.

Example 4

Repeated example 1. In the resulting high-boiling fraction was added 1 wt.% solid hydroxide natsproektam on distillation column with five theoretical plates continuously taken out of equilibrium. The yield of caprolactam was 74%, in the calculation of the high-boiling fraction, so that the total yield of caprolactam in the calculation of the original nitrile 6-aminocaproic acid was 93%.

1. The method of obtaining caprolactam by reacting solution of nitrile 6-aminocaproic acid with water in the liquid phase at elevated temperature, characterized in that (a) an aqueous solution of nitrile 6-aminocaproic acid in the liquid phase without the addition of catalyst is heated in the reactor And the mixture I consisting mainly of water, caprolactam, and the high-boiling fraction, then (b) water from a mixture of I are removed from the mixture II, consisting mainly of caprolactam and high-boiling fraction, then (C) from a mixture of II by distillation separately produce caprolactam and high-boiling fraction, then (G1) high-boiling fraction from step (C) is served in the reactor And on the stage (a) or (G2) high-boiling fraction is similar stage (a) is heated in the second reactor B and then treated similarly to the stages (b) and (C) additional amounts of caprolactam, or (G3) high-boiling fraction under reduced pressure in the presence of a base heated in the reactor and leaving the reaction mixture is subjected to distillation with poslati take from 10 to 150 mol of water.

3. The method according to p. 1 or 2, characterized in that the reaction mixture in stage (a) add an organic solvent.

4. The method according to PP.1 to 3, characterized in that the reaction in the reactor And is carried out at a temperature of 200 to 370oC.

5. The method according to PP.1 to 4, characterized in that the reaction in the reactor And are under pressure of 0.1 - 50 MPa.

6. The method according to PP.1 to 5, characterized in that the reaction time in the reactor And is 20 to 180 minutes

 

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