How providerone of dinitriles to aminonitriles

 

(57) Abstract:

The invention relates to a method of providerone of dinitriles to the appropriate aminonitriles using hydrogen and a catalyst selected from Raney Nickel, Raney cobalt and Raney Nickel contains one activating element selected from elements of groups IVb, VIb, VIIb and VIII of the Periodic system of elements and zinc, and cobalt, Raney contains one activating element selected from elements of groups IVb, VIb, VIIb and VIII of the Periodic system of elements and zinc, and in the presence of a strong inorganic bases - derived alkaline or alkaline earth metal, namely, what source environment hydrogenation contains in the absence of any other solvent water at the rate of 0.5 - 20 wt.% in relation to the total number of liquid components of the reaction medium, the diamine and/or aminonitriles formed from gidrirovannogo of dinitrile and untransformed dinitrile, on the basis that all three compounds comprise from 80 to 99.5 wt.% in relation to the total number of liquid components of the environment, while achieving the degree of conversion of dinitrile constituting 95%, and achieving selectivity for aminonitriles at least 60%. gidrirovaniya of dinitriles to the appropriate aminonitriles.

Typically, the hydrogenation dinitrile is carried out to obtain the corresponding diamines; in particular, the hydrogenation of adiponitrile results diamine, which is one of two major compounds in obtaining 6,6-polyamide.

However, it is sometimes necessary to obtain a diamine, and an intermediate aminonitriles. To do this, but not only, conduct providerone adiponitrile to aminoacetonitrile, which can then be transformed into caprolactam, which is the starting compound to obtain 6-polyamide, or directly to a 6-polyamide.

In the patent US 4389348 described method of hydrogenation of dinitrile to omega-aminonitriles using hydrogen in the environment aprotic solvent and ammonia, in the presence of rhodium on a carrier.

In the patent US 5151543 describes how partial hydrogenation of dinitrile to aminonitriles in molar excess solvent to dinitrile average of at least 2/1, using liquid ammonia or alkanol containing inorganic base, soluble in this alkanol, in the presence of catalyst, type of Nickel or Raney cobalt.

In patent WO-A-93/16034 describes how to obtain 6-aminocaproate the oxide of the alkali metal or ammonium, complex low valent transition metal and Nickel Raney catalyst. The implementation of this method is in accordance with examples, in a solvent such as lower alkanol or hydrocarbon.

The present invention relates to a preferred hydrogenation of one of the nitro function dinitrile (herein called providerone) to obtain the most appropriate aminonitriles and in the least amount of diamine.

More specifically, the invention concerns a method of providerone aliphatic dinitriles to the appropriate aminonitriles using hydrogen and a catalyst selected from Raney Nickel, Raney cobalt and Raney Nickel contains one activating element selected from elements of groups IVb, VIb, VIIb and VIII of the Periodic system of the elements, published in the Handbook of Chemistry and Physics (Weast, 5 edition de 1970-1971), and zinc, and cobalt, Raney contains one activating element selected from elements of groups IVb, VIb, VIIb and VIII of the Periodic system of elements and zinc, and in the presence of a strong inorganic base, which is derived from alkali or alkaline earth metal, and the method is characterized by the fact that:

- IP is idca compounds of this environment, the diamine and/or aminonitriles able to form of gidrirovannogo of dinitrile and untransformed dinitrile, estimated that all three compounds comprise from 80-99,5 wt.% in relation to the total number of liquid components of the environment

the degree of conversion of dinitrile can reach 95%,

and selectivity for the target aminonitriles is not less than 60%.

The degree of conversion of dinitrile preferably at least 70%.

Aliphatic dinitrile that can be used in the method according to the invention are, in particular, dinitrile General formula (I)

NC-R-CN,

where R is alkylene or Alcanena, linear or branched, containing from 1 to 12 carbon atoms.

Preferably, in the method of the invention uses dinitrile formula (I), where R is a linear or branched alkylene containing 1-6 carbon atoms.

As examples of such dinitriles you can lead, in particular, adiponitrile, methylglutaronitrile, ethylsuccinate, malononitrile, succinonitrile and glutaronitrile and their mixtures, in particular mixtures of adiponitrile, and/or methylglutaronitrile, and/or ethylsuccinate that may come with one is then found, as corresponds to adiponitrile (ADN), used as an example in this way.

Strong inorganic base, mainly selected from hydroxides, carbonates, and alkanoates alkali or alkaline earth metal. It is chosen, preferably, from hydroxides, carbonates, and alkanoates alkali metal.

Preferably a strong inorganic base selected from the following compounds: LiOH, NaOH, KOH, RbOH, CsOH, and mixtures thereof.

Practically, most use of NaOH and KOH, due to the best combination of technical characteristics and prices, despite the fact that RbOH and CsOH can also give very good results.

The composition of the reaction medium may vary depending on the type of the method of the invention.

Indeed, under the periodic method, the method, as, in particular, in the laboratory or in small periodic production, the initial reaction medium is gradually enriched by aminonitriles and, to a lesser extent, diamine, whereas the concentration of dinitrile may or decrease, if at the beginning of providerone is the number of or most of this dinitrile or remain regarding the implementation of the method, the composition of the reaction medium at the outlet of the reactor reaches a value determined by the selectivity of the reaction.

Usually, the presence of water is 20% or below. Preferably, the water content in the reaction medium ranges from 2 to 15 wt.% in relation to the total number of liquid components of the above environment.

The concentration of the target aminonitriles and/or the corresponding diamine and untransformed dinitrile in the reaction medium is generally from 85 to 98 wt.% in relation to the total number of liquid components above the reaction medium.

In the continuous method, the method of the invention, the composition at the outlet of the reactor is determined by the ratio of the values of the relative selectivity of aminonitriles and diamine and the rate of introduction of dinitrile.

The number of strong inorganic bases, preferably greater than or equal to 0.1 mol/kg of catalyst. Preferably, it is from 0.1 mol to 3 mol/kg of catalyst, and most preferably from 0.2 to 2 moles of catalyst.

For optimum selectivity aminonitriles, the ratio of a strong inorganic base and catalyst may vary depending on the and, in particular, Raney Nickel, activated or not activated.

The catalyst used in the method may be Raney Nickel, Raney cobalt and Raney Nickel or Raney cobalt contains, in addition to Nickel or cobalt and residual quantities of metal to be removed from the original alloy upon receipt of the catalyst, typically aluminum, one or more other elements, called activators, such as chromium, titanium, molybdenum, tungsten, iron, zinc. Among these activators most preferred are chromium, titanium, iron, and mixtures thereof. The content of these activators in relation to Nickel or cobalt in wt.%, typically, ranges from 0 to 15%, preferably from 0 to 10%.

In the presence of a catalyst activator, such as chromium or titanium, it is useful to consider the ratio of strong base to activator. Preferably use a ratio of KOH/activator from 12 to 30 moles per kg of activator and the ratio of NaOH/activator from 12 to 50 moles per kg of activator.

The amount of catalyst may vary slightly depending, in particular, the method works or selected reaction conditions. So, if dinitrile postepenno, what if all of dinitrile was introduced at the beginning of the reaction. For example, you can use 0.5 to 50 wt.% catalyst by weight of the total reaction medium, and often 1-35 wt.%.

For a given catalyst and a given degree of conversion dinitrile, the output of aminonitriles reaches a maximum and is determined by the ratio base/Ni or Foundation/Co-selected in the above ranges of values.

The overall selectivity of aminonitriles improved by increasing the rate constants for the hydrogenation of dinitrile to aminonitriles, not when the reduction of the rate constants for the hydrogenation of aminonitriles to the diamine. It is the rate constant for the first of two consecutive reactions affect the above various parameters.

The method according to the invention, as a rule, carried out at the reaction temperature below or equal to 150oC, preferably lower than or equal to 120oC and, in particular, less than or equal to 100oC.

More specifically, this temperature is from ambient temperature (approximately 20 theoC) to 100oC.

Before, during or after heating, the reaction chamber is set to an appropriate hydrogen pressure, i.e. about 1 bar (0,10 Met the reaction conditions and catalyst.

When the periodic method, it can vary from several minutes to several hours.

With the continuous method is preferred in industrial conditions of the method, the duration is not clearly defined parameter.

It should be noted that the expert can modify the sequence of steps of the method according to the invention depending on the operating conditions.

Other conditions for hydrogenation (continuous or batch method) according to the invention are conventional and known in themselves.

The following examples illustrate the present invention.

In the examples the following abbreviations are used:

- ADN - adiponitrile

- AKN - aminocaproate

- GMI - hexamethylenediamine were

- TT - degree conversion

- RT - selectivity with respect to the transformed source connection (here in relation to the ADN).

Example 1

In the reactor of stainless steel with a volume of 300 ml, equipped with a stirrer type Rushtone cavitator, means for introducing reagents and hydrogen, and the temperature control system type g:

Adiponitrile - 95,1

Hexamethylenediamine were - 94 which I Raney. The reaction mixture is heated to 50oC after purge of nitrogen through the reactor, then hydrogen; set pressure of 2 MPa at this temperature by the continuous feed of hydrogen. The reaction is monitored by the consumption of hydrogen and chromatographic analyses in the aqueous phase (CPG) of the reaction mixture. When reaching the optimal value of the output, the reaction is stopped by stopping the stirring and cooling the reaction mixture.

Get the following results:

- duration of reaction - 80 min

- TT ADN - 83.5% OF

- RT DCA - 77.5% OF

Example 2

Repeat example 1 under the same operating conditions but with the following input composition, g:

Adiponitrile - 95,1

Hexamethylenediamine were - 95,4

Water to 21.1

CON - 0,113

The Raney-Nickel (from 1.7% Cr) - 2,5

In this example, 0,8 mol KOH/kg of Raney Nickel.

Get the following results:

- duration of reaction - 80 min

- TT ADN - 81,9%

- RT DCA - 68,3%

Example 3

Repeat example 1 under the same operating conditions but with the following input components, g:

Adiponitrile - 27,4

Hexamethylenediamine were - 166,4

Water and 19.4

CON - 0,115

The Raney-Nickel (from 1.7% Cr) - 2,5

In this example, 0,8 what BR>
- TT ADN 71.2 PERCENT

- RT DCA - 77,0%

Example 4

Repeat example 1 under the same operating conditions but with the following input components, g:

Adiponitrile - 142,4

Hexamethylenediamine were - 47,75

Water to 21.1

CON - 0,053

The Raney-Nickel (from 1.7% Cr) - 2,5

In this example, the use of 0.4 mol of KOH/kg of Raney Nickel.

Get the following results:

- duration of reaction - 103 min

- TT ADN IS 76.2%

- RT DCA FOR 77.2%

Example 5

Repeat example 1 under the same operating conditions but with the following composition, g:

Adiponitrile - 95,1

Hexamethylenediamine were with 97.1

Water to 21.1

KOH - 0,056

The Raney-Nickel (from 2.4% Cr, 1.3% Fe) - 2,5

In this example, the use of 0.4 mol of KOH/kg of Raney Nickel and 16.7 moles KOH/kg Cr.

Get the following results:

- duration of reaction - 45 min

- TT ADN - 82,4%

- RT DCA - 74,3%

Example 6

Repeat example 1 under the same operating conditions but with the following composition, g:

Adiponitrile - 95,0

Hexamethylenediamine were - 97,3

Water to 21.1

CON - 0,056

The Raney-Nickel (with 3.0% of Cr and 1.6% Fe) - 2,5

In this example, the use of 0.4 mol of KOH/kg of Raney Nickel and 13.3 moles KOH/kg Cr.

Receive the following financial p is the PR of stainless steel with a capacity of 150 ml, equipped with magnetic stirrer, means for introducing reagents and hydrogen and a temperature regulation system, enter:

Adiponitrile - 21,65

Hexamethylenediamine were - 21,65

Water - 4,75

NaOH - 0,0372

The Raney-Nickel (from 1.7% Cr) - 0,58

In this example, the use of 1.6 mol NaOH/kg of Raney Nickel.

The reaction mixture is heated to 50oC after passing through the reactor with nitrogen, then hydrogen, install a pressure of 2 MPa at this temperature by the continuous introduction of hydrogen. The reaction course is monitored by the consumption of hydrogen and chromatographic analyses in the aqueous phase (CPG) of the reaction mixture. When reaching the optimal value of the output, the reaction is stopped by stopping the stirring and cooling the reaction mixture.

Get the following results:

- duration of response - 90 min

- TT ADN - 70%

- RT DCA - 62%

Example 8

Repeat example 7 under the same operating conditions but with the following input components, g:

Adiponitrile - 21,6

Hexamethylenediamine were - 21,8

Water - 4,75

NaOH - 0,0046

The Raney-Nickel (from 1.7% Cr) - 0,58

In this example, the use of 0.2 mol NaOH/kg of Raney Nickel.

Get the following results:

- PR is x the same operating conditions, but with the following composition, g:

Adiponitrile - 21,6

Hexamethylenediamine were - 21,7

Water - 4,78

NaOH - 0,0094

The Raney-Nickel (from 1.7% Cr) - 0,58

In this example, the use of 0.4 mol NaOH/kg of Raney Nickel.

Get the following results:

- duration of reaction - 67 min

- TT ADN - 80%

- RT DCA - 69%

Example 10

Repeat example 7 under the same operating conditions but with the following composition, g:

Adiponitrile - 21,6

Hexamethylenediamine were - 21,6

Water - 4,75

NaOH - 0,0187

The Raney-Nickel (from 1.7% Cr) - 0,58

In this example, 0,8 mol NaOH/kg of Raney Nickel.

Get the following results:

- duration of reaction - 69 min

- TT ADN - 75%

- RT DCA - 73%

Example 11

Repeat example 7 under the same operating conditions but with the following composition, g:

Adiponitrile - 21,65

Hexamethylenediamine were - 21,65

Water - 4,75

KOH - 0.026

The Raney-Nickel (from 3.6% Cr) - 0,58

In this example, 0,8 mol KOH/kg of Raney Nickel.

Get the following results:

- duration of reaction - 51 min

- TT ADN - 75%

- RT DCA - 67%

Example 12

In a metal reactor equipped with a stirrer type Cavitator, medium, is 2856

Hexamethylenediamine were - 1151

Water - 588

CON - 0,83

The Raney-Nickel (from 1.7% Cr) - 37

Operate in the conditions described for example 1.

Get the following results:

- duration of response to 3 h 30 min

- TT ADN - 86%

- RT DCA - 64%

Example 13

In the reactor of stainless steel with a capacity of 150 ml, equipped with a magnetic stirrer, means for introducing reagents and hydrogen and a temperature regulation system, enter:

Adiponitrile - 6

Hexamethylenediamine were - 41,16

Water - 0,84

CsOH - 0,054

The Raney-Nickel (12% Fe) - 0,4

In this example, the use of 0.9 mol of CsOH/kg of Raney Nickel.

The reaction mixture is heated to 80oC after passing through the reactor with nitrogen, then hydrogen, install a pressure of 2.5 MPa at this temperature by the continuous introduction of hydrogen. Over the course of the reaction is observed in the consumption of hydrogen and chromatographic analysis in the aqueous phase (CPG) of the reaction mixture. When reaching the optimal value of the output, the reaction is stopped by stopping the stirring and cooling the reaction mixture.

Get the following results:

- duration of response 50 min

- TT ADN - 89%

- RT DCA - 65%

Example 14

Hexamethylenediamine were - 37,8

Water - 4.2V

CsOH - being 0.036

The Raney Nickel (1.5% Ti) - 0,4

In this example, the use of 0.6 mole of CsOH/kg of Raney Nickel.

Get the following results:

- duration of response - 20 min

- TT ADN - 90%

- RT DCA - 60%e

1. How providerone saturated dinitriles to the appropriate aminonitriles using hydrogen and a catalyst selected from Raney Nickel and Raney cobalt and Raney Nickel contains one or more activators selected from elements of groups IVb, VIb, VIIb and VIII of the Periodic system of elements and zinc, and cobalt, Raney contains one or more activators selected from elements of groups IVb, VIb, VIIb and VIII of the Periodic system of elements and zinc, and in the presence of inorganic bases - derived alkaline or alkaline earth metal, characterized in that what source environment hydrogenation contains in the absence of any other solvent water at the rate of 0.5-20 wt.% in relation to the total number of liquid components of the reaction medium, the diamine and/or aminonitriles formed from gidrirovannogo of dinitrile, as well as unreacted dinitrile, on the basis that all three compounds comprise from euromania of dinitrile, reaching 95%, and the selectivity for aminonitriles at least 60%.

2. The method according to p. 1, characterized in that the degree of transformation of dinitrile is at least 70%.

3. The method according to p. 1 or 2, characterized in that the inorganic base selected from the hydroxides, carbonates and alkanoates alkali or alkaline earth metal, preferably, from hydroxides, carbonates, and alkanoates alkali metal.

4. The method according to p. 1 or 3, characterized in that the strong inorganic base selected from the following compounds LiOH, NaOH, KOH, RbOH, CsOH and mixtures thereof.

5. The method according to p. 1 or 4, characterized in that the amount of inorganic base in the reaction medium is greater than or equal to 0.1 mol / kg of catalyst, preferably from 0.1 to 3 moles per kg of catalyst.

6. The method according to p. 1 or 5, characterized in that the amount of inorganic bases KOH, RbOH and CsOH in the reaction medium is from 0.2 to 1.0 mole per kg of catalyst, in particular, activated or non-activated Raney Nickel.

7. The method according to p. 1 or 5, characterized in that the amount of inorganic bases NaOH, LiOH in the reaction medium ranges from 0.2 to 1.5 moles per kg produce the clinical topics what use aliphatic dinitrile General formula I

NC-R-CN

where R is alkylene, linear or branched, containing from 1 to 12 carbon atoms, preferably R is a linear or branched alkylene containing 1-6 carbon atoms.

9. The method according to p. 1 or 8, characterized in that the amount of water in the reaction medium ranges from 2 to 15 wt.% in relation to the total number of liquid components in this environment.

10. The method according to p. 1 or 9, characterized in that the concentration of the target aminonitriles and/or the corresponding diamine and unreacted dinitrile in the reaction medium ranges from 85 to 98 wt.% in relation to the total number of liquid components of the reaction medium.

11. The method according to p. 1 or 10, characterized in that the used catalyst selected from Raney Nickel and Raney cobalt and Raney Nickel and Raney cobalt contain one or more activators, such as chromium, titanium, molybdenum, tungsten, iron, zinc.

12. The method according to p. 1 or 11, characterized in that the catalyst is Raney Nickel containing at least one activator selected from chromium, titanium, iron, and mixtures thereof.

 

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