The method of simultaneous receipt of caprolactam and diamine

 

(57) Abstract:

Adipodinitrile partially hydronaut obtaining a mixture containing mainly 6-aminocaproate, hexamethylenediamine were, ammonia, adipodinitrile, hexamethylenimine, then distilling produce hexamethylenediamine were and 6-aminocaproate. Last cyclist in caprolactam. From the reaction mixture from stage hydrogenation is separated by distillation incompletely ammonia leading product and CBM product I, containing mainly 6-aminocaproate, hexamethylenediamine were, adipodinitrile, hexamethylenimine. The distillation is carried out in the presence of inert substances A. Then CBM product I is subjected to distillation to obtain a mixture of inert matter and ammonia in the form of a downstream product, and cubic product II, containing mainly 6-aminocaproate, hexamethylenediamine were, adipodinitrile, hexamethylenimine and inert substance A. In the third column of the cubic product II release a substance And as head of product and CBM product III, which is subjected to distillation in the fourth column with getting head product containing mainly hexamethylenimine sent optionally further purification in the fifth column, where they are provided with cages least 95%. CBM product of the fourth column contains mostly 6-aminocaproate and adipodinitrile, is subjected to distillation in the sixth column of obtaining as head of product 6-aminoacetonitrile with a purity of at least 95%, which is then cyclist in caprolactam. As a result, in the same process combines the two-stage process caprolactam from adiponitrile through simultaneous production of 6-aminocaproate and its cyclization. 5 C.p. f-crystals, 1 Il.

The present invention relates to a method of simultaneously obtaining caprolactam and diamine, based on adipodinitrile.

Further, the invention relates to an improved method of simultaneous selection 6-aminocaproate and diamine containing these compounds mixture.

Partial hydrogenation of adipodinitrile 6-aminocaproate in the presence of ammonia and various catalysts already widely described. Thus, in U.S. patent 4601859 describe the use of catalysts based on rhodium oxide of magnesium, in U.S. patent 2762835 described the use of Raney Nickel, in U.S. patent 2208598 describes the use of Nickel on aluminum oxide, tiled application Germany 848654 described catalysts in a fixed bed based on copper/cobalt/zinc and by the application of Germany 4235466 described the use of sponge iron.

As described in WO 92/21650 the method are in the presence of Raney Nickel outputs aminoacetonitrile 60% when the degree of conversion of 70% and outputs diamine 9%. When the degree of conversion 80% yield is 62%.

Further, it is known that 6-aminocaproate turns with water in the gas or liquid phase, in the presence of catalysts or without them, with the liberation of ammonia in caprolactam. Thus, in U.S. patent 2301964 described the way that 10-25% solution of 6-aminocaproate converted into caprolactam in the liquid phase at a temperature of 250-290oC with outputs of up to 76%.

Further, in the application France 2029540 described cyclization of 25-35% solutions 6-aminocaproate at 220oC in the liquid phase in water with the addition of organic solvents in the presence of zinc compounds, copper, lead, and mercury. Thus receive the outputs of caprolactam to 83%.

The cyclization of 6-aminocaproate can also be performed in the gas phase (U.S. Pat. USA 2357484): based on 80% of the energy of aqueous solutions prepared at 305oC with alumina as catalyst caprolactam yield 92%.

In the application for the European patent 150259 described the transformation of 6-aminocaproate in the gas phase in the presence of copper-vanadium catalysts, the 134 described the transformation in caprolactam, 6-aminocaproate in the water in the liquid phase without a catalytic Converter.

Of these publications does not follow the way of obtaining caprolactam from adipodinitrile through 6-aminocaproate, in which both stages are combined in one process.

Therefore, the objective of the invention was to develop a method to simultaneously obtain caprolactam and diamine, based on adipodinitrile. Next, it was necessary to develop a method which would give from the reaction mixture obtained by the partial hydrogenation of adipodinitrile, in a continuous process of pure 6-aminocaproate and hexamethylenediamine were, and 6-aminocaproate should cilitates in the next stage of the caprolactam. Then, the obtained in this way by-products should be as recyclable and it is preferable to return to an earlier stage.

In line with this, a method was found to simultaneously obtain caprolactam and diamine, based on adipodinitrile, according to which

a) adipodinitrile partially hydronaut obtaining a mixture containing mainly 6-aminocaproate, hexamethylenediamine were, ammonia, adipodinitrile, hexamethylenimine, and

b) obtained in stage a) the mixture is subjected to distillation to obtain ammonia as the head product and the cubic proteinurea in the conditions of the distillation of substances And, boiling at a pressure of 18 bar at a temperature of from 60 to 220oC, the ammonia is separated incompletely, and

C) CBM product I, containing mainly 6-aminocaproate, hexamethylenediamine were, adipodinitrile, hexamethylenimine, inert substance A and ammonia, and ammonia is lower than in the mixture introduced at stage b), is subjected to a second distillation to obtain a mixture of inert substances A and ammonia as the head product and cubic product II, and the distillation is carried out at a temperature Cuba from 100 to 220oC and a pressure of from 2 to 15 bar, provided that the pressure in the first and second distillation columns so consistent with each other, so that when the temperature of the cube 220oC the temperature at the head of the column was higher than the 20oC, and

g) CBM product II, containing mainly 6-aminocaproate, hexamethylenediamine were, adipodinitrile, hexamethylenimine and inert substance A, is subjected to distillation in the third column of receipt of inert substances in the form of A head product and cubic product III, and distillation is carried out at a temperature of Cuba from 100 to 220oC and a pressure of from 0.1 to 2 bar, provided that obtained as the head product of the inert substance is A fail on the second column, and when Neji 0.3 bar at a temperature of from 50 to 220oC,

d) CBM product III, containing mainly 6-aminocaproate, hexamethylenediamine were, adipodinitrile, hexamethylenimine and, if necessary, an inert substance B, is subjected to distillation in the fourth column with the receiving head of product GP containing mainly hexamethylenimine, if necessary, an inert substance B and hexamethylenediamine were, and will be retrieved when the temperature of the cube from 100 to 220oC and a pressure of from 10 to 500 mbar, and the cubic product IV,

e) head product GP is subjected to distillation in the fifth column of the receiving head of product GP containing mainly hexamethylenimine and, if necessary, an inert substance B, and retrieved when the temperature of the cube from 100 to 220oC and a pressure of from 50 to 2000 mbar, and the cubic product V, containing mainly hexamethylenediamine were of a purity of at least 95%, and the head product GP serves, if necessary partially to the third column and the remainder output, and

g) CBM IV product, containing mainly 6-aminocaproate and adipodinitrile, is subjected to distillation in the sixth column of obtaining as head of product 6-aminoacetonitrile with a purity of at least 95% and adipodinitrile in the form of the cubic product, and the-aminocaproate cyclist in caprolactam.

Hereinafter, a method was found for the simultaneous selection of 6-aminocaproate and diamine containing from their mixtures.

Partial hydrogenation of adipodinitrile can be performed by any of known methods described above and are described, for example, in U.S. patent N 4601859; 2762835; 2208598; in tiled applications Germany N 848654; 954416; 4235466 or in the international application WO 92/21650, by conducting the hydrogenation in the presence of Nickel-, cobalt-, iron - or registergui catalysts. This can be used as solid catalysts, and catalysts on the media. As carriers can be used alumina, silicon dioxide, titanium dioxide, magnesium oxide, activated carbon, and spinel. As solid catalysts, such as Raney Nickel and Raney cobalt.

Usually choose the load of the catalyst is from 0.05 to 10, preferably from 0.1 to 5 kg adipodinitrile per 1 liter of catalyst per hour.

The hydrogenation is conducted usually at a temperature of from 20 to 200, preferably from 50 to 150oC and a partial pressure of hydrogen of 0.1 to 20, preferably from 0.5 to 10 MPa.

The hydrogenation is conducted preferably in the presence of a solvent, in particular ammonia. Co">

Molar ratio of 6-aminocaproate to hexamethylenediamine were and thus caprolactam to hexamethylenediamine were can be adjusted accordingly to a selected degree of conversion of adipodinitrile. Preferably operate at a degree of conversion of adipodinitrile from 10 to 80, preferably from 30 to 60%, in order to obtain high selectivity to 6-aminocaproate.

Typically, the amount of 6-aminocaproate and diamine is depending on the catalyst and reaction conditions of from 95 to 99%, with a significant number byproduct is hexamethylenimine.

According to a preferred form of execution of the invention, the transformation is carried out in the presence of ammonia and lithium hydroxide, or lithium compounds, giving under the reaction conditions lithium hydroxide, at a temperature of from 40 to 120, preferably from 50 to 100, even more preferably from 60 to 90oC; pressure choose from 2 to 12, preferably from 3 to 10, even more preferably from 4 to 8 MPa. The reaction time depends mainly on the desired yield, the selectivity and degree of conversion; it is usually chosen so as to achieve the maximum output current, for example, from 50 to 275, preferably from 70 to 200 minutes.

Ammonia is usually introduced in such quantity that the weight ratio of ammonia to dinitrile ranged from 9:1 to 0.1:1, preferably from 2.3:1 to 0.25:1, particularly preferably from 1.5:1 to 0.4:1.

The amount of lithium hydroxide is chosen usually from 0.1 to 20, preferably from 1 to 10 wt.%, counting on the amount of the catalyst.

As lithium compounds, giving under the reaction conditions lithium hydroxide, should be called: metallic lithium, alkyl and aryl compounds of lithium, for example n-utility and finality. The amounts of these compounds are chosen so that formed above the amount of lithium hydroxide.

As the catalyst used is preferably Nickel, ruthenium, rhodium and cobalt containing compounds, preferably of the Raney type, in particular Raney Nickel and Raney cobalt. You can also use catalysts on carriers, and carriers can be, for example, aluminum oxide, silicon dioxide, zinc oxide, activated carbon or titanium dioxide (see Appl. Het. Cat. , 1987, pp. 106-122; Catalysis, I. 4 (1981) pp. 1-30). Especially preferred is a Raney-Nickel (e.g., companies BASF AG, Degussa and grace).

Nickel, ruthenium, rhodium and cobaltites, Rh, Ir, Pd, Pt) of the Periodic system of elements. According to the observations using, in particular, as a catalyst of Raney Nickel, modified, for example, chromium and/or iron, leads to higher selectivity on aminonitriles (see getting posted in the application of Germany 2260978; Bull. Soc. Chem. 13 (1946), page 208).

The amount of catalyst is chosen so that the quantity of cobalt, ruthenium, rhodium or Nickel ranged from 1 to 50, preferably from 5 to 20 wt.%, counting on the entered dinitrile.

The catalysts can be used in a fixed bed method of feeding on the bottom or method of irrigation, or preferably in the form of a suspension catalysts.

According to another preferred form of execution of the invention adipodinitrile partially hydronaut 6-aminocaproate at elevated temperature and elevated pressure in the presence of solvent and catalyst, and using a catalyst containing

(a) compound based on a metal selected from the group consisting of Nickel, cobalt, iron, ruthenium and rhodium and

(b) from 0.01 to 25, preferably from 0.1 to 5 wt.%, counting on (a), of a promoter based on a metal selected from the group consisting of palladium, platinum, irawo, phosphorus, arsenic, antimony, bismuth and rare earth metals, and

(C) from 0 to 5, preferably from 0.1 to 3 wt.%, counting on (a), compounds based on alkali or alkaline earth metal,

provided that if the component (a) is a connection on the basis of ruthenium or rhodium, or ruthenium, and rhodium, or Nickel and rhodium, the promoter (b) may be missing.

The preferred catalysts are those in which component (a) contains at least one compound based on a metal selected from the group: Nickel, cobalt and iron, in an amount of from 10 to 95 wt.%, and ruthenium and/or rhodium in an amount of from 0.1 to 5 wt.%, counting on the sum of components (a) to (C),

component (b) contains at least one promoter based on a metal selected from the group of silver, copper, manganese, rhenium, lead, aluminum and phosphorus in amounts of from 0.1 to 5 wt.%, counting on (a), and

component (b) contains at least one connection based on the alkali and alkaline earth metal selected from the group of lithium, sodium, potassium, cesium, magnesium and calcium in an amount of from 0.1 to 5 wt.%, counting on (a).

Preferred are the following catalysts:

the catalyst And containing 90 wt.% nitric oxide is the catalyst B, containing 20 weight. % of cobalt oxide (CoO), 5 wt.% manganese oxide (Mn2O3), 0.3 wt.% silver oxide (Ag2O), 70 wt.% silicon dioxide (SiO2), 3.5 weight. % of aluminum oxide (Al2O3), 0.4 wt.% iron oxide (Fe2O3), 0.4 wt.% magnesium oxide (MgO), and 0.4 wt.% of calcium oxide, and

the catalyst containing 20 wt.% the Nickel oxide (NiO), 67,42% wt. silicon dioxide (SiO2), 3.7 wt.% aluminum oxide (Al2O3), 0.8 wt.% iron oxide (Fe2O3), 0,76% wt. magnesium oxide (MgO), 1.92 wt.% calcium oxide (CaO), 3.4 wt.% of sodium oxide (Na2O), and 2.0 wt% potassium oxide (K2O).

If used according to the invention catalysts we are talking about massive catalysts or catalysts on the media. As carriers can be used, for example, porous oxides, such as aluminum oxide, silicon dioxide, lanthanum oxide, titanium dioxide, zirconium dioxide, magnesium oxide, zinc oxide and zeolites, and activated carbon or mixtures thereof.

Receiving occurs, as a rule, so that the precipitated precursor of component (a) with a precursor of a promoter component (b) and optionally with the forerunners of the microcomponents (C) in the presence or in the absence of the of Isadora processed into rods or tablets, dried and then calcined. Catalysts on the media are also usually the fact that the carrier is impregnated with a solution of components (a), (b) and optionally (C), and individual components may be added simultaneously or sequentially, or by spraying with known methods of components (a), (b) and optionally (C) to the media.

Predecessors of the component (a) are, as a rule, are water soluble salts of the above metals, such as nitrates, chlorides, acetates, formate and sulfate, preferably nitrates.

Predecessors of the component (b) are, as a rule, are water soluble salts or complex salts of the above metals, such as nitrates, chlorides, acetates, formate and sulfate, as well as, in particular, hexachloroplatinate, preferably nitrates and hexachloroplatinate.

Predecessors of the component (b) are, as a rule, are water soluble salts of the above alkali and alkaline earth metals, such as hydroxides, carbonates, nitrates, chlorides, acetates, formate and sulfate, preferably hydroxides and carbonates.

Precipitation usually occurs from aqueous solutions, possibly by adding osdetect usually at a temperature of from 80 to 150oC, preferably from 80 to 120oC.

The calcination is conducted usually at a temperature of from 150 to 500oC, and in some cases use temperatures of up to 1000oC, preferably from 200 to 450oC in a stream of air or nitrogen.

After annealing the obtained catalyst mass is exposed to a reducing agent (activation), for example, it is subjected to treatment with hydrogen or a gas mixture containing hydrogen and an inert gas, for example nitrogen, at a temperature of from 80 to 250oC, preferably from 80 to 180oC, for the catalysts based on ruthenium or rhodium as the component (a), or at a temperature of from 200 to 500, preferably from 250 to 400oC for catalysts based on a metal selected from the group: Nickel, cobalt and iron, as component (a) for 2-24 hours. The loading of the catalyst is thus preferably from 100 to 300, particularly preferably 200 l per 1 l of catalyst.

It is preferred to carry out the activation of the catalyst inside the reactor for synthesis, because it isn't necessary in other cases, an intermediate stage, namely, the passivation of the surface usually at a temperature of from 20 to 80, what's catalysts produce then in the reactor for synthesis at a temperature of from 180 to 500oC, preferably from 200 to 350oC, in an atmosphere containing hydrogen.

You can use the catalyst in a fixed bed method of feeding on the bottom or method of irrigation, or as suspension catalysts.

If the transformation is carried out in suspension, then select temperature from 40 to 150, preferably from 50 to 100, even more preferably from 60 to 90oC.

The pressure is usually selected from 2 to 20, preferably from 3 to 10, particularly preferably from 4 to 9 MPa. The residence time in the reaction zone depends mainly on the desired yield, the selectivity and degree of conversion. Usually this time is chosen such as to achieve maximum output, for example, from 50 to 275, preferably from 70 to 200 minutes.

During the suspension the way work is used as solvent, preferably ammonia, amines, diamines and triamine with 1-6 carbon atoms, such as trimethylamine, triethylamine, Tripropylamine and tributylamine, or alcohols, in particular methanol and ethanol, particularly preferred is ammonia. It is advisable to choose the concentration of dinitrile from 10 to 90, preferably from 30 to 80, more preferably from 40 to 70 wt.%, considering the amount of dinitrile and solvent.

Suspension hydrogenation can be performed periodically, however, preferred is a continuous conduction, usually in the liquid phase.

Partial hydrogenation can also be performed continuously or periodically on a fixed catalyst method of irrigation or recharge from below, and the temperature is usually selected from 20 to 150, preferably from 30 to 90oC and a pressure of from 2 to 30, preferably from 3 to 20 MPa. According to the invention the partial hydrogenation is carried out in the presence of a solvent, preferably ammonia, amines, diamines and triamines with 1-6 carbon atoms, such as trimethylamine, triethylamine, Tripropylamine and tributylamine, or alcohol, preferably methanol and ethanol, particularly preferably ammonia. According to a preferred form of execution of ammonia choose from 1 to 10, preferably from 2 to 6 g per 1 g of adipodinitrile. The load of the catalyst is chosen from 0.1 to 2.0, preferably from 0.3 to 1.0 kg adipodinitrile per liter of catalyst per hour. Increasing the reaction time can be varied specifically the degree of conversion and the selectivity.

Partial hydrogenation can be carried out in the usual, adapted to ethologie a), contains mostly 6-aminocaproate, hexamethylenediamine were, ammonia, adipodinitrile, hexamethylenimine, preferably a mixture containing mainly

from 1 to 70, preferably from 5 to 40 wt.% 6-aminocaproate,

from 1 to 70, preferably from 5 to 40 wt.% adipodinitrile,

from 0.1 to 30, preferably from 0.5 to 20 wt.% diamine,

from 0.01 to 10, preferably from 0.05 to 5 wt.% hexamethylenimine and

from 5 to 95, preferably from 20 to 85 wt.% ammonia (and the sum of all components must be 100%), at a temperature of Cuba from 60 to 220, preferably from 100 to 200oC and a pressure of from 10 to 30, preferably from 12 to 25 bar in the presence of inert under the conditions of the distillation of substances And which boils at a pressure of 18 bar at a temperature of from 60 to 220oC, obtaining ammonia as head of product and cubic product I, and the ammonia is separated incompletely.

As substances And use according to the invention such substances which are inert under the distillation conditions and have a boiling point of from 60 to 220oC, preferably from 60 to 150oC at a pressure of 18 bar. As an example, should be called alkanes, cycloalkanes, aromatic hydrocarbons, naphthenes, alcohols, about the 2-4 carbon atoms, especially preferred are n-pentane, cyclohexane, triethylamine, ethanol, acetonitrile, n-hexane, di-n-propyl simple ether, isopropanol, n-butylamine, benzene, even more preferred is ethanol.

Usually substance a is added in an amount of from 0.1 to 50, preferably from 1 to 10 wt.%, counting on CBM product I.

In stage C) CBM product I, containing mainly 6-aminocaproate, hexamethylenediamine were, adipodinitrile, hexamethylenimine, inert matter and ammonia, and ammonia is lower than in the mixture introduced to the step (b) from stage a), is subjected to a second distillation to obtain a mixture of inert substances and ammonia as the head product and cubic product II, and the distillation is carried out at a temperature Cuba from 100 to 220oC and a pressure of from 2 to 15 bar, under the condition that the pressure in the first and second distillation column (K2 in the drawing) are consistent with each other, so that when the temperature of the cube 220oC the temperature at the head of the column was higher than the 20oC.

In stage g) CBM product II, containing mainly 6-aminocaproate, hexamethylenediamine were, adipodinitrile, hexamethylenimine and inert substance And is subjected to distillation in the third column (which the PMC is carried out at a temperature of Cuba from 100 to 220oC, preferably from 140 to 200oC and a pressure of from 0.1 to 2 bar, preferably from 0.2 to 1 bar, provided that obtained as the head product is an inert substance And served in the second column, and, if necessary, distillation is carried out in the presence of inert under the conditions of the distillation of substances B, boiling at a pressure of 0.3 bar and a temperature of from 50 to 220oC, preferably from 60 to 150oC.

As the substance B should be called alkanes, cycloalkanes, aromatic hydrocarbons, naphthenes, alcohols, ethers, NITRILES and amines with the above properties, in particular di-n-butyl simple ether, valeronitrile, n-octane, cyclooctane, n-hexylamine, hexamethylenimine, especially preferred is hexamethylenimine.

According to a preferred form of execution of the invention, the substance B use hexamethylenimine, however, it is most preferable not to add substance B.

Substance B is added in an amount of from 0.1 to 50, preferably from 0.5 to 10 wt.%, counting on CBM product II.

In stage d) CBM product III, containing mainly 6-aminocaproate, hexamethylenediamine were, adipodinitrile, hexamethylenimine and, if necessary, in the 1, containing mainly hexamethylenimine, if necessary, an inert substance B and hexamethylenediamine were, and will be retrieved when the temperature of the cube from 100 to 220oC, preferably from 140 to 200oC and a pressure of from 10 to 500 mbar, preferably from 40 to 200 mbar, and the cubic product IV.

In stage e) of the parent product GP is subjected to distillation in the fifth column (K5 in the drawing) to obtain the head of product GP containing mainly hexamethylenimine and, if necessary, an inert substance B, and retrieved when the temperature of the cube from 100 to 220oC, preferably from 140 to 200oC and a pressure of from 50 to 2000 mbar, preferably from 300 to 1000 mbar, and the cubic product V, containing mainly hexamethylenediamine were of a purity of at least 95%, preferably from 99 to 99.9%, and the head product GP serves, if necessary partially to the third column and the remainder of the display.

With the release of a portion of the product GP, which basically consists of hexamethylenimine and, if necessary, the substance B, preferably only from hexamethylenimine, if not add substance B or is hexamethylenimine (see phase g), it is possible to avoid accumulation of hexamethylenimine and Vestel, is subjected to distillation in the sixth column (K6 in the drawing) with the receipt as head of product 6-aminoacetonitrile with a purity of at least 95%, preferably from 99 to 99.9% and adipodinitrile in the form of the cubic product, and the distillation is carried out at a temperature Cuba from 100 to 220oC, preferably from 140 to 200oC and a pressure of from 1 to 500 mbar, preferably from 5 to 100 mbar.

Received 6-aminocaproate cyclist in caprolactam. This cyclization is conducted by known methods in liquid or gas phase, for example, according to the method according to U.S. patent 2301964 and 2357484, European patent application 150295 or tiled application Germany 4319134, what usually 6-aminocaproate subjected to transformation with water in liquid phase to obtain caprolactam and ammonia.

In the case of the promotion without catalyst choose a temperature from 200 to 375oC and the reaction time from 10 to 90, preferably from 10 to 30 minutes. The solvent used is usually water, the content of 6-aminocaproate, in the calculation of the water, usually less than 30, preferably from 10 to 25 wt.%.

When turning in the liquid phase in the presence of a catalyst temperature is usually selected from 50 to 330oC, the amount of water the city to several hours. When using an organic solvent, in particular ethanol, the amount of water ranges from 1.3 to 5 moles per mole of 6-aminocaproate.

Obtained by cyclization of the reaction product is first distilled, while the separated ammonia, water and organic solvent, if he had. Located in the bottom product of the catalyst, if it were, separated from caprolactam by known methods and are returned to the reactor for cyclization (P2 in the drawing). Crude caprolactam by known methods, for example by distillation, transferred to pure caprolactam, which is then used for polymerization in polycaprolactam.

According to a preferred form of execution of the invention 6-aminocaproate turn with water in the liquid phase using heterogeneous catalysts.

The interaction is carried out in the liquid phase is typically at a temperature of from 140 to 320oC, preferably from 160 to 280oC. the Pressure is usually from 1 to 250 bar, preferably from 5 to 150 bar, it should be taken that the reaction mixture under these conditions, the predominant part of it was liquid. The transformation time is usually from 1 to 120, preferably from 1 to 90, in particular from 1 to 60 minutes. Sometimes is preferably 0.1 to 20, and in particular, from 1 to 5 mol of water.

It is preferable to use 6-aminocaproate in the form of 1 to 50% by weight, in particular 5-50% by weight, more preferably 5-30% by weight solution in water (and in this case, the solvent is simultaneously reagent) or in mixtures of water/solvent. The solvent includes, for example, alcohols such as methanol, ethanol, n - and isopropanol, n-, ISO - and tert.butanol, polyols such as diethylene glycol and tetraethylene glycol, hydrocarbons such as petroleum ether, benzene, toluene, xylene, lactams, such as pyrrolidone or caprolactam, or the alkyl substituted lactams, such as N-organic N-methylcaprolactam or N-ethylcaproic, as well as esters of carboxylic acids, preferably carboxylic acids with 1 to 8 carbon atoms. The reaction may also be present ammonia. Can also be used a mixture of organic solvents. Especially preferred in some cases are a mixture of water and alcohol in a weight ratio of water/alcohol 1-75/25-99, preferably 1-50/50-99.

Also is it possible to use 6-aminocaproate both as a reagent and as a solvent.

As hetaerae retia or fourth main group of the Periodic system of elements, such as calcium oxide, magnesium oxide, boron oxide, aluminum oxide, tin oxide or silicon dioxide in the form of pyrogene obtained silicon dioxide, silica gel, kieselguhr, quartz or mixtures thereof, further, the oxides of metals of the second to sixth subgroups of the Periodic system of elements, such as titanium oxide, amorphous or in the form of anatase or rutile, zirconium oxide, zinc oxide, manganese oxide, or mixtures thereof. Can also be used oxides of the lanthanides and actinides, cerium oxide, thorium oxide, praseodymium oxide, samarium oxide, mixed oxides of rare earth metals or mixtures thereof with the above-mentioned oxides. Other catalysts can be, for example, oxides of vanadium, iron, chromium, molybdenum, tungsten or mixtures thereof. It is also possible mixtures of the aforementioned oxides with each other. You can also apply some of the sulfides, selenides and tellurides, such as zinc telluride, selenide, tin, molybdenum sulfide, tungsten sulfide, sulfides of Nickel, zinc and chromium.

The above compounds may contain additives compounds of the first and the seventh main group of the Periodic system of elements.

Further, as suitable catalysts ledue is UP>.

If necessary, these catalysts can contain up to 50 wt.% copper, tin, zinc, manganese, iron, cobalt, Nickel, ruthenium, palladium, platinum, silver or rhodium.

Depending on their composition catalysts can be used in the form of solid or catalyst on the carrier. Thus, the titanium dioxide can be used in the form of rods or supported on a carrier in a thin layer. For the deposition of titanium dioxide on the media, such as silicon oxide, aluminum oxide or zirconium dioxide, applicable all described in the literature methods. So, may be applied to a thin layer of titanium dioxide by hydrolysis technologicheskij compounds such as isopropylate titanium or butyl titanium, or by hydrolysis of titanium tetrachloride or other inorganic titanium containing compounds. Can also be used brines containing titanium dioxide.

Other suitable compounds are chloride zirconyl, aluminum nitrate and cerium nitrate.

Suitable carriers are powders, rods or pellets of the above mentioned oxides or other stable oxides, such as silicon dioxide. In order to improve the transfer of substances carriers can be made of macroporous.

As suitable solvents should be called aliphatic alcohols with 1-4 carbon atoms, for example methanol, ethanol, n-propanol, isopropanol, butanol, glycols, such as ethylene glycol, diethylene glycol, triethylene glycol, tetraethylene glycol, ethers, such as methyl-tert.-butyl ether, diethyl ether of diethylene glycol, alkanes with 6-10 carbon atoms, such as n-hexane, n-heptane, n-octane, n-nonan, n-decane, and cyclohexane, benzene, toluene, xylene, lactams, such as pyrrolidone, caprolactam or N-alkyla ctam.

According to another form of execution of the invention to the reaction mixture from 0 to 5, preferably from 0.1 to 2 wt.% ammonia, hydrogen or nitrogen.

The reaction is carried out at a temperature of from 200 to 370, preferably from 220 to 350oC, particularly preferably from 240 to 320oC.

Usually the reaction is carried out under pressure, and the pressure is chosen from 0.1 to 50, preferably from 5 to 25 MPa, to the reaction mixture was preferably in the liquid phase.

The duration of the reaction depends mainly on the selected parameters of the method and when a continuous process is usually from 20 to 180, preferably from 20 to 90 minutes. Reduction of the time generally decreases the degree of transformation, with increasing time are formed, according to the observations, interfering oligomers.

The cyclization preferably carried out continuously in a tubular reactor, a reactor with a stirrer or in combinations thereof.

The cyclization can be conducted periodically. The duration of the reaction is usually from 30 to 180 minutes.

Obtained after the reaction mixture consists mainly of 50-98, preferably 80-95 weight. % water, and from 2 to 50, preferably from 5 to 20 wt.% a mixture consisting of 50-90, prepost predpochtitelnei form of execution of the invention removed after partial hydrogenation and after separation of ammonia and inert matter (CBM product column 3) possible dust catalyst and non-volatile high-boiling components by evaporation, when this undesirable substances remain in Cuba.

According to another preferred form of execution of the invention of the cubic product column 6, containing adipodinitrile and high-boiling components are distilled adipodinitrile and bring it on stage a), it is also possible from the cube columns 6 to print the partial stream.

According to another form of execution of the invention can CBM product III sum of the fourth column, the distillation is conducted in such a way as to obtain as the head product hexamethylenimine and, if necessary, the substance B, and CBM product IV. The part of the product return in column III, the remainder of the release, to avoid accumulation.

CBM product IV down to the fifth column and distilled under such conditions, to obtain hexamethylenediamine were in the form of the head of the product and a bottoms distillation residue V. This VAT residue V down to the sixth string and get 6-aminocaproate as head of product and adipodinitrile as residue.

Distillation in the fourth column named according to the last form of the invention is conducted preferably at a temperature of Cuba from 100 to 220, preferably from is named according to the last form of the invention is conducted preferably at a temperature of Cuba from 100 to 220, preferably from 140 to 200oC and a pressure of from 10 to 500, preferably from 40 to 200 mbar.

Distillation in the sixth column named according to the last form of the invention is conducted preferably at a temperature of Cuba from 100 to 220, preferably from 140 to 200oC and a pressure of from 10 to 500, preferably from 5 to 100 mbar.

Further processing of the product obtained according to this preferred form of carrying out the invention and containing hexamethylenediamine were, 6-aminocaproate and adipodinitrile, carried out similarly to the proposed method.

According to another preferred form of execution of the invention is removed by distillation of high-boiling VAT residue III before it is served on the fourth column. Thereby, it is possible to avoid the separation of high-boiling cube columns containing adipodinitrile.

Obtained according to the invention hexamethylenediamine were you clear on conventional methods and used for polymers and copolymers, for example of polyamide-66.

According to the invention can be part of the method of obtaining caprolactam from adipodinitrile also be used for simultaneous separation of 6-aminocaproate, hexamethylene the Yu mostly 6-aminocaproate, hexamethylenediamine were, ammonia, adipodinitrile, hexamethylenimine, is subjected to distillation to obtain ammonia as head of product and VAT residue I, and the distillation is carried out at a temperature Cuba from 60 to 220oC and a pressure of from 10 to 30 bar in the presence of inert under the conditions of the distillation of substances And boiling at a pressure of 18 bar, at a temperature of from 60 to 220oC, the ammonia is separated incompletely, and

b) CBM product I, containing mainly 6-aminocaproate, hexamethylenediamine were, adipodinitrile, hexamethylenimine, inert matter and ammonia, and ammonia is lower than in the mixture introduced in stage a), is subjected to a second distillation to obtain a mixture of inert substances and ammonia as the head product and cubic product II, and the distillation is carried out at a temperature Cuba from 100 to 220oC and a pressure of from 2 to 15 bar, under the condition that the pressure in the first and second distillation columns so consistent with each other, so that when the temperature of the cube 220oC the temperature at the head of the column was higher than the 20oC, and

C) VAT II product containing mainly 6-aminocaproate, hexamethylenediamine were, adipodinitrile, hexamethylenimine and inert substance And is subjected to distillation in treeko carried out at a temperature Cuba from 100 to 220oC and a pressure of from 0.1 to 2 bar, provided that obtained as the head product is an inert substance And down on the second column, and, if necessary, distillation is carried out in the presence of inert under the conditions of the distillation of substances B, boiling at a pressure of 0.3 bar at a temperature of from 50 to 220oC,

g) CBM product III, containing mainly 6-aminocaproate, hexamethylenediamine were, adipodinitrile, hexamethylenimine and, if necessary, an inert substance B, is subjected to distillation in the fourth column with the receiving head of product GP containing mainly hexamethylenimine, if necessary, an inert substance B and hexamethylenediamine were, and will be retrieved when the temperature of the cube from 100 to 220oC and a pressure of from 10 to 500 mbar, and the cubic product IV,

d) head product GP is subjected to distillation in the fifth column of the receiving head of product GP containing mainly hexamethylenimine and, if necessary, an inert substance B and retrieved when the temperature of the cube from 100 to 220oC and a pressure of from 50 to 2000 mbar, and the cubic product V, containing mainly hexamethylenediamine were of a purity of at least 95%, and the head product GP serves, if necessary partially to the third number, is subjected to distillation in the sixth column of obtaining as head of product 6-aminoacetonitrile with a purity of at least 95% and adipodinitrile in the form of the cubic product, and the distillation is carried out at a temperature Cuba from 100 to 220oC and a pressure of from 1 to 500 mbar.

The advantage of the method according to the invention is that it became available method for continuous receipt of caprolactam, based on adipodinitrile, while gaining diamine.

Examples

Example 1

a) Hydrogenation of adipodinitrile 6-aminocaproate

In an autoclave with stirrer hydronaut a mixture of 4,6 kg adipodinitrile (ADN), 4.6 kg of ammonia, 0.45 kg of suspended Raney Nickel (H 1-50, BASF) and 8 g of lithium hydroxide at 80oC, the total pressure of 70 bar within 1 hour (the partial pressure of hydrogen is 4 bar). The hydrogenation product after separation of Raney Nickel has the following composition: 2.5 kg ADN, 2 kg 6-aminocaproate (DCA), 0.2 kg diamine (GMI), 10 g of hexamethyleneimine (GMO) and 4.5 kg of ammonia.

b) Distillation of the hydrogenation product

Freed from catalyst product after hydrogenation stage (a) serves at the head of the first column with two theoretical plates. is deposits in stage a).

VAT residue of the first column, ethanol and a small amount of ammonia, the reaction mixture is served at the temperature of the cube 180oC in the second column with 13 theoretical plates.

From the head of this column 0.4 kg of a mixture of 25 wt.% ammonia and 75 wt.% ethanol return at the 50oC and 10 bar in the first column.

CBM product of the second column containing 30 wt.% ethanol and 30 ppm of ammonia and having a temperature of 180oC is fed to a third column with 14 theoretical plates. From the head of this column divert 50oC and a pressure of 300 mbar to 2 kg of ethanol and return the second column.

From the cube to the third pillar, which has a temperature of 180oC, output 4.8 kg of product with the content of hexamethylenimine (GMO) 2 wt.% and served on the fourth column with 20 theoretical plates. From the head of this column divert 90oC and 85 mbar 0.3 kg product with a content of 65 wt.% GMI, 35 wt.% GMS and 1000 ppm DCA.

The removal of the head of the fourth column serves on the fifth column 15 theoretical plates. At 114oC and 500 mbar output as the head of product 90 g GMO content GMI 1000 ppm and return to the third column. VAT product Codey served on the sixth column 15 theoretical plates. From the head of this column divert at 111oC and 15 mbar 2 kg DCA containing 1,000 ppm of the GMI and 100 ppm ADN and removed from the process. From the head of column release 2.5 kg ADN with 500 ppm DCA.

b) Cyclization of 6-aminocaproate in caprolactam

A solution of 2 kg of DCA (stage b)), 0.64 kg of water and 17.4 kg of ethanol miss at 230oC and 80 bar for 15 minutes in hot oil, filled with bars of titanium dioxide (4 mm) of the reactor (the ratio of length to diameter = 100). The reaction product contains 1.8 kg of caprolactam, 0.05 kg of the ethyl ester of 6-aminocaproic acid, 0.04 kg 6-aminocaproate (determined by gas chromatography), and 0.11 kg of 6-aminocaproic acid and oligomers, i.e., polymers of caprolactam (determined by high-performance liquid chromatography). Fractional distillation get 1.7 kg of caprolactam.

Example 2

a) Hydrogenation of adipodinitrile 6-aminocaproate

Tubular reactor with a length of 2 m and an internal diameter of 2.5 cm fill 750 ml (1534) catalyst consisting of 90 wt.% of cobalt oxide, 5 wt.% manganese oxide, 3 wt.% phosphorus pentoxide and 2 wt.% of sodium oxide, and the catalyst is activated within 48 hours in a stream of hydrogen (500 l/h) without pressure povyshenie in the reactor down at 200 bar (total pressure) of the mixture of 380 g/hour adipodinitrile, 380 g/h of ammonia and 500 l/h of hydrogen. Additionally for heat dissipation cycle is four times the number of inflow (about 3 kg/hour). Adipodinitrile turns at 60%. The reaction mixture consists of 50 wt.% ammonia, 20 wt.% ADN, 18 wt.% AKN, to 11.9 wt.% GMI, 0.05 wt.% GM, 0.05 wt.% other (preferably high-boiling). (DCA-selectivity: 60% DCA + GMI-selectivity: > 99%).

b) Distillation of the hydrogenation product

10 kg of the hydrogenation product from stage a) is served at the head of the first column with two theoretical plates. From the head of column isolate the 47oC and 19 bar 5,0 kg of ammonia 20 ppm DCA and used for the hydrogenation in stage (a).

VAT residue of the first column, ethanol and a small amount of ammonia, the reaction mixture is served at the temperature of the cube 180oC in the second column with 10 theoretical plates.

From the head of this column 1.2 kg of a mixture of 30 wt.% ammonia and 70 wt.% ethanol return at the 50oC and 10 bar in the first column.

CBM product of the second column containing 40 wt.% ethanol and 90 ppm of ammonia and having a temperature of 177oC is fed to a third column with 10 theoretical plates. From the head part of this is BA the third column, which has a temperature of 180oC, output 5,0 kg of product with the content of hexamethylenimine (GMO) of 0.55 wt.% and served on the fourth column with 20 theoretical plates. From the head of this column divert 90oC and 85 mbar 1.22 kg of product with the content of 97.8 wt.% GMI, 2.2 wt.% GMS and 1000 ppm DCA.

The removal of the head of the fourth column serves on the fifth column 15 theoretical plates. At 114oC and 500 mbar output as the head of product 26 g GMO content GMI 1000 ppm, of which 22 g return to the third column. CBM product containing at 177oC 1.19 kg GMI and 100 ppm lags, is removed from the process.

CBM product from the fourth column serves on the sixth column 15 theoretical plates. From the head of this column divert at 111oC and 15 mbar 1.8 kg DCA containing 1,000 ppm of the GMI and 100 ppm ADN and removed from the process. From the head of column release 2.0 kg ADN with 500 ppm DCA.

b) Cyclization of 6-aminocaproate in caprolactam

A solution of 2 kg of DCA (from example 2B)), 0.64 kg of water and 17.4 kg of ethanol miss at 230oC and 80 bar for 15 minutes in hot oil, filled with bars of titanium dioxide (4 mm) of the reactor (the ratio of length to diaminobiphenyl (determined by gas chromatography), and 0.11 kg of 6-aminocaproic acid and oligomers, i.e., polymers of caprolactam (determined by high-performance liquid chromatography).

Fractional distillation get 1.7 kg of caprolactam.

1. The method of simultaneous receipt of caprolactam and diamine, characterized in that a) the initial mixture containing mainly 6-aminocaproate, hexamethylenediamine were, ammonia, adipodinitrile, hexamethylenimine, is subjected to distillation to obtain ammonia as head of product and cubic product I, and the distillation is carried out at a temperature Cuba from 60 to 220oC and a pressure of from 10 to 30 bar in the presence of inert under the conditions of the distillation of substances And boiling at a pressure of 18 bar at a temperature of from 60 to 220oC, the ammonia is separated incompletely, and (b) CBM product I, containing mainly 6-aminocaproate, hexamethylenediamine were, adipodinitrile, hexamethylenimine, inert matter and ammonia, and ammonia is lower than in the mixture introduced in stage a), is subjected to a second distillation to obtain a mixture of inert substances and ammonia as the head product and cubic product II, and the distillation is carried out at a temperature Cuba from 100 to 220oC and a pressure of from 2 to 15 bar is the temperature value of the cube 220oC the temperature at the head of the column was higher than the 20oC, and b) CBM product II, containing mainly 6-aminocaproate, hexamethylenediamine were, adipodinitrile, hexamethylenimine and inert substance And is subjected to distillation in the third column of receipt of inert substances And as head of product and cubic product III, and distillation is carried out at a temperature of Cuba from 100 to 220oC and a pressure of from 0.1 to 2 bar, provided that obtained as the head product is an inert substance And down on the second column, and, if necessary, distillation is carried out in the presence of inert under the conditions of the distillation of substances B, boiling at a pressure of 0.3 bar at a temperature of from 50 to 220oC, g) CBM product III, containing mainly 6-aminocaproate, hexamethylenediamine were, adipodinitrile, hexamethylenimine and, if necessary, an inert substance B, is subjected to distillation in the fourth column with the receiving head of product GP containing mainly hexamethylenimine, if necessary, an inert substance B and hexamethylenediamine were, and will be retrieved when the temperature of the cube from 100 to 220oC and a pressure of from 10 to 500 mbar, and the cubic product IV, d) head product GP is subjected to distillation in the fifth column of photo B and retrieved when the temperature of the cube from 100 to 220oC and a pressure of from 50 to 2000 mbar, and the cubic product V, containing mainly hexamethylenediamine were of a purity of at least 95%, and the head product GP serves, if necessary, only partially on the third column and the remainder of the display, and (e) CBM IV product, containing mainly 6-aminocaproate and adipodinitrile, is subjected to distillation in the sixth column of obtaining as head of product 6-aminoacetonitrile with pure, at least 95% and adipodinitrile in the form of the cubic product, moreover, the distillation is carried out at a temperature Cuba from 100 to 220oC and a pressure of from 1 to 500 mbar, and then the obtained 6-aminocaproate cyclist in caprolactam.

2. The method according to p. 1, wherein the initial mixture obtained by partial hydrogenation of adipodinitrile.

3. The method according to PP.1 and 2, characterized in that the cubic product of the sixth column contains adipodinitrile and high-boiling, distillation separates adipodinitrile and return to the stage partial hydrogenation of adipodinitrile.

4. The method according to PP.1 to 3, characterized in that use the original mixture, consisting mainly of 1 to 70 wt.% 6-aminocaproate, 1 to 70 wt.% adipodinitrile, 0.1 to 30 wt.% diamine, 0.01 to 10 wt.% hexane is causesa fact, as inert substance And use ethanol.

6. The method according to PP. 1 to 5, characterized in that as component B use hexamethylenimine.

 

Same patents:

The invention relates to the production of aliphatic lactams, in particular E-caprolactam used in the production of polyamides

The invention relates to the production of modified layered silicates and can be used in the manufacture of paints, coating of enamel, plaster, household paints, ceramic industry for obtaining anhydrous molding compounds, as active fillers in polymers and rubbers, for lubricating and cooling fluids, drilling fluids oil-based

-alkoxyalkyl)caprolactam with protecting and aerorepublica activity" target="_blank">

The invention relates to new biologically active compounds, namely N-(-alkoxyalkyl)caprolactam General formula

NH - OC6H13where R is H, CH3with insect - and aerorepublica activity

-alkoxyalkyl)caprolactam with insectrepellent activity" target="_blank">

The invention relates to new biologically active compounds, namely N-(-alkoxyalkyl)caprolactam General formula

NH - OR1where R=C3H7when R1=C2H5-C4H9with insectrepellent activity

The invention relates to the production of aliphatic lactams, in particular E-caprolactam used in the production of polyamides

The invention relates to a new process for the preparation of cyclic lactams by reacting NITRILES aminocarbonyl acid with water in the presence of catalysts

The invention relates to a method of catalytic hydrogenation of NITRILES to amines
The invention relates to the field of catalytic hydrogenation of NITRILES to amines, and in particular dinitriles, such as adiponitrile to diamines, such as hexamethylenediamine were

The invention relates to a method of catalytic hydrogenation of NITRILES to amines
The invention relates to the field of catalytic hydrogenation of NITRILES to amines, and in particular dinitriles, such as adiponitrile to diamines, such as hexamethylenediamine were

The invention relates to a method of selective hydrogenation dinitrile compounds of General formula NC-(CH2)nCN, where n= 1-6, in the presence of a catalyst containing a metal of the 8th group of the Periodic system of the elements Nickel and a zeolite having a pore size diameter from 0.3 to 0.7 nm, preferably 0.3 to 0.5 nm

The invention relates to methods for secondary aliphatic amine is di-n-Propylamine (DPA), which is used as intermediate in obtaining herbicides of type "treflan", "litre" and others, is the raw material in the synthesis of perforated dielectric - heat transfer fluids used in the manufacture of advanced products everyday and special electronic equipment, etc

FIELD: industrial organic synthesis.

SUBSTANCE: process comprises hydrogen reduction of halogenated aromatic nitrile represented by general formula 1:

in which X denotes chlorine or fluorine atom, m integer from 1 to 5, n integer from 1 to 5, and m+n ≤ 5, provided than when n≥ 2, all X can be the same or different, using hydrogenation catalyst selected from group consisting of optionally modified porous nickel and optionally modified porous cobalt and in presence of organic acid in solvent to form halogenated aromatic methylamine represented by general formula 2: , in which X, m, and n are as defined above and "a" is integer from 1 to m).

EFFECT: enabled efficient large-scale production of desired product with high output.

20 cl, 7 ex

FIELD: industrial organic synthesis.

SUBSTANCE: invention relates to continuous process for hydrogenation of compounds containing nitrile and nitro groups to produce amino or aminonitrile compounds in presence of heterogeneous hydrogenation catalyst and a basic compound. Into reactor, at stirring, are fed: first stream of reactant to be hydrogenised, second stream of catalyst, third stream of alkali compound, fourth stream of hydrogen to maintain hydrogen pressure in reactor. From reactor is withdrawn at least fifth stream composed of reaction mixture and containing hydrogen bubbles dispersed therein. Fifth stream circulates in at least one circulation circuit coming out of lower section into top section of reactor. Fifth stream remove excess heat released in hydrogenation reaction and so temperature of reaction mixture is maintained below 150°C. Fifth stream circulating in one of circuits is passed through filter medium to produce sixth stream containing a part of hydrogenate separated from catalyst. From reactor and one of circulation circuit, seventh stream is picked and sent to liquid and solid phase separation stage to produce liquid phase comprised of hydrogenate without catalyst and catalyst-containing solid phase. The latter is subjected to reduction before being recycled into the second catalyst stream fed into reactor.

EFFECT: increased selectivity and productivity of hydrogenation process and enabled reduction and reuse of catalyst.

18 cl, 2 dwg

FIELD: organic chemistry, chemical technology.

SUBSTANCE: invention relates to a method for synthesis of primary amine by the hydrogenation reaction of nitriles. Method involves carrying out the conversion reaction in reaction mixture that contains: (a) at least one nitrile; (b) hydrogen; (c) ammonia, if necessary, and (d) at least one cobalt or nickel catalyst modified ex situ by adsorption of alkaline metal carbonate or alkaline metal hydrocarbonate that comprises alkaline metal carbonate or hydrocarbonate taken in the amount from 2 to 12 wt.-%. Also, invention relates to a catalyst used in the method by cl. 1 and representing modified cobalt or nickel catalyst prepared by adsorption of alkaline metal carbonate or alkaline metal hydrocarbonate taken in the amount from 2 to 12 wt.-% on usual cobalt or nickel catalyst.

EFFECT: improved method of synthesis.

24 cl, 6 tbl, 48 ex

Up!