Title of Invention	METHOD FOR MAKING METHYLPENTAMETHYLENEDIAMINE AND METHYLPIPERIDINE
Abstract	The present invention relates to a method for making methyl-2-pentamethylene diamine and methyl-3-piperidine.The invention particularly relates to a method for making methyl-2-pentamethylene diamine and methyl-3-piperidine by hydrogenation of methyl-glutaronitrile.The method according to the invention comprises carrying out hydrogenation in the presence of a catalyst including cobalt, chromium and nickel. More specifically , the catalysat is based on Raney cobalt doped with nickel and chromium.

Title of Invention

METHOD FOR MAKING METHYLPENTAMETHYLENEDIAMINE AND METHYLPIPERIDINE

Abstract

The present invention relates to a method for making methyl-2-pentamethylene diamine and methyl-3-piperidine.The invention particularly relates to a method for making methyl-2-pentamethylene diamine and methyl-3-piperidine by hydrogenation of methyl-glutaronitrile.The method according to the invention comprises carrying out hydrogenation in the presence of a catalyst including cobalt, chromium and nickel. More specifically , the catalysat is based on Raney cobalt doped with nickel and chromium.

Full Text	Method for making methylpentamethylenediamine and methylpiperidine [0001] The present invention relates to a process for the manufacture of 2-methylpentamethylenediamine and of 3-methylpiperidine. [0002] It relates to a process for the manufacture of 2-methylpentamethylenediamine and 3-methylpiperidine by hydrogenation of methylglutaronitrile. [0003] Methylglutaronitrile is a compound obtained in conjunction with adiponitrile in the process for the hydrocyanation of butadiene. It is already known to convert this methylglutaronitrile to methylpentamethylenediamine (MPMD) by hydrogenation in the presence of various catalysts, such as Raney cobalt or Raney nickel. High degrees of conversion of methylglutaronitrile to MPMD have been obtained by using pure methylglutaronitrile and by carrying out the hydrogenation under high pressures, as is described in French patents 2 306 202 and 2 306 203. [0004] A description has also been given of processes for the hydrogenation of methylglutaronitrile to give a mixture of 2-methylpentamethylenediamine (MPMD) and 3-methylpiperidine (MPP) with catalysts based on nickel or Raney nickel under high hydrogen pressures. Such processes have been described in particular in French patents 2 306 204, 2 306 205, 2 306 206, 2 306 207 and 2 306 208. The proportion of MPMD formed with respect to the MPP is variable, depending on the solvent and/or the catalyst used. As for the processes described above, these processes use a pure ethylglutaronitrile (MGN) compound as starting material. A process for the hydrogenation of pure MGN to give MPMD and MPP in the presence of Raney cobalt doped with chromium has also been proposed by patent US 4 885 391. This reaction is advantageously carried out in the presence of water. The degree of conversion of the MGN to give products of economic value, namely MPMD and MPP, is at most 85%, with formation of approximately 10% of heavy products not of economic value. [0005] 2-Methylpentamethylenediamine (MPMD) is used mainly in two applications, one as monomer for the manufacture of polyamide, in total or partial replacement of hexamethylenediamine, the other as starting material in the manufacture of β-picoline, which is itself a synthetic intermediate in manufacturing nicotinamide. This process is described in the literature, for example in the paper by S. Lanini and R. Prins published in Appl. Cat. A, 1996, 137, pp 287-306, under the title "Synthesis of 3-picoline from MGN over supported noble metals catalysts". [0006] The proposal has also been made to synthesize β-picoline by ehydrogenation of a mixture of 2-methyl-pentamethylenediamine and 3-methylpiperidine, as described in patent US 4 401 819. [0007] Furthermore, methylglutaronitrile is mainly produced in the process for the manufacture of adiponitrile, a synthetic intermediate in the manufacture of hexamethylenediamine and caprolactam, which are important monomers in the production of polyamides. [0008] Methylglutaronitrile is separated from adiponitrile by distillation and recovered in the form of a distillation fraction. In fact, the fraction recovered is a mixture of dinitrile compounds comprising predominantly methylglutaronitrile and a few percent of ethylsuccinonitrile and of adiponitrile. [0009] An additional distillation is necessary in order to obtain pure methylglutaronitrile, a product used in the hydrogenation processes of the prior art. The tests described in patent US 4 521 602 show that the conversion of MGN to 3-methylpyridine is obtained with a yield of 80% starting from pure MGN and only 42% with a mixture of dinitriles. [0010] In addition, the processes for the conversion of MGN to MPMD and MPP described in the literature use high hydrogen pressures in order to obtain a percentage of conversion of MGN to MPMD+MPP of greater than 90%. Hydrogenation reaction is often carried out in the liquid medium. [0011] In order to make it possible to lower the cost of manufacture of β-picoline, it is important to look for solutions which make it possible to carry out the conversion of MGN either in the pure form or present in the mixture of dinitriles with high yields for conversion of MGN to MPMD and MPP of greater than 90% and under milder operating conditions than those described in the prior art. [0012] One of the aims of the present invention is to provide a process for the manufacture of 2-methylpenta-methylenediamine and 3-methylpiperidine from pure methylglutaronitrile or methylglutaronitrile as a mixture with other nitriles with high degrees of conversion to MPMD + MPP, these two compounds being of economic value in downstream processes for the manufacture of important chemical compounds, such as (3-picoline, as indicated above. [9913] To this end, the invention provides a process for the manufacture of 2-methylpentamethylenediamine and 3-methylpiperidine by hydrogenation of methylglutaronitrile, characterized in that the hydrogenation is carried out in the presence of a catalyst comprising cobalt and, as doping elements, chromium and nickel at an absolute hydrogen pressure of less than 50 bar, preferably of less than 40 bar, advantageously of between 10 and 35 bar. [0014] According to another characteristic of the invention, the hydrogenation is carried out in the presence of a solvent chosen from the group preferably consisting of alcohols, water or a mixture of these. It is also possible to use, as solvent, one of the compounds resulting from the hydrogenation reaction (MPMD and/or MPP), in combination with water. [0015] Advantageously, the hydrogenation is carried out in the presence of a strong basic inorganic compound chosen from the group consisting of alkali metal hydroxides and ammonium hydroxide. Preferably, the basic compound is potassium hydroxide or aqueous ammonia. [0016] The hydrogenation can be carried out at a temperature of between 60 and 160°C, advantageously between 80 and 140°C. [0017] According to a novel characteristic of the invention, the catalyst comprises an amount of cobalt, expressed as elemental Co, of between approximately 85% and approximately 98% of the total weight of the catalyst, an amount of nickel, expressed as elemental Ni, of between approximately 0.1% and approximately 4% by weight of the catalyst and an amount of chromium, expressed as elemental Cr, of between approximately 0.1% and approximately 4% by weight of the catalyst. [0018] According to a preferred characteristic of the invention, the cobalt present in the catalyst is a Raney cobalt. [0019] The catalyst of the invention makes it possible to obtain a very high degree of conversion of MGN to MPMD and MPP of approximately 100% and thus to avoid the formation of a large amount of heavy compounds or compounds having a high boiling point, as was obtained with the catalysts of the state of the art. [0020] In addition, according to another advantage of the process of the invention using a catalyst with a specific composition, it is possible to use, as starting material to be hydrogenated, a mixture of dinitriles comprising methylglutaronitrile, ethyl-succinonitrile and adiponitrile. This mixture of dinitriles advantageously corresponds to the distillation fraction produced in the process for the manufacture of adiponitrile by double hydrocyanation of butadiene, making it possible to separate the branched dinitriles (methylglutaronitrile, ethylsuccinonitrile) from adiponitrile. [0021] This mixture of dinitriles generally has the following composition by weight: Methylglutaronitrile : of between 70% and 95% Ethylsuccinonitrile : of between 5% and 30% Adiponitrile : of between 0% and 10%. [0022] Thus, the process of the invention makes it possible to obtain a high degree of conversion of the MGN present in this mixture to give MPMD and MPP. [0023] According to a preferred characteristic of the invention, the mixture of dinitriles can be enriched in methylglutaronitrile before feeding to the hydrogenation stage, for example by distillation. [0024] 2-Methylpentamethylenediamine, 3-methyl-piperidine or their mixtures can be used as starting materials in the manufacture of β-picoline according to the processes described in the documents already mentioned above. [0025] In the embodiment of the invention using a mixture of dinitriles as starting materials, it is possible to use the compounds resulting from the hydrogenation directly in the process for the manufacture of β-picoline, without separation and purification of the MPMD and MPP. However, it may be preferable to carry out a separation of these two compounds from the other products resulting from the hydrogenation of ESN or AdN. This separation can be carried out by any known technique and in particular distillation. [0026] Other advantages and details of the invention will be illustrated by the examples given below solely by way of illustration. [0027] Example 1, comparative (pure MGN): 2 g of catalyst based on Raney nickel comprising 91% by weight of nickel and doped with 2% by weight of Cr are added to 100 g of a 20% by weight solution of MGN (99% purity) in ethanol and 1.5 g of NH3 in the form of an aqueous NH4OH solution comprising 28% by weight of NH3. The reactor is purged with nitrogen and then with hydrogen. The reaction medium is heated under hydrogen pressure and is stirred when the desired temperature is reached (100°C). The reactor is cooled in order to keep the temperature of the medium at approximately 100°C. The relative pressure in the reactor is kept constant at a value of 25 bar. When the hydrogen is no longer being consumed, the mark of the end of the reaction, a sample of the reaction medium is withdrawn for analysis by gas chromatography. [0028] The results of the analysis show that MGN is completely converted and that the selectivity for MPMD is 23% and that for MPP is 44%. The sum of the selectivities for products of economic value is thus 67%. [0029] Example 2 of the invention (pure MGN): 2 g of catalyst based on Raney cobalt comprising 92% by weight of cobalt and doped with 2.2% by weight of Cr and 2.4% by weight of Ni are added to 100 g of a 20% by weight solution of MGN (99% purity) in ethanol and 1.5 g of NH3 in the form of an aqueous NH4OH solution comprising 2 8% by weight of NH3. The reactor is purged with nitrogen and then with hydrogen. The reaction medium is heated under hydrogen pressure and is stirred when the desired temperature is reached (100°C). The reactor is cooled in order to keep the temperature of the medium at approximately 100°C. The pressure in the reactor is kept constant at a value of 25 bar. When the hydrogen is no longer being consumed, the mark of the end of the reaction, a sample of the reaction medium is withdrawn for analysis by gas chromatography. [0030] The results of the analysis show that the MGN is completely converted and that the selectivity for MPMD is 80% and that for MPP is 20%. The sum of the selectivities for products of economic value is thus 100%. [0031] The degree of conversion of the MGN to MPMD and MPP is notably higher than that obtained in example 1 with a catalyst based on Raney nickel but also than that shown in patent US 4 885 391. Specifically, this document describes the hydrogenation of MGN to give MPMD and MPP in the presence of a chromium-doped Raney cobalt catalyst. The maximum degree of conversion is of the order of 80 to 85% with the formation of compounds of high boiling point representing approximately 10% of the products obtained. [0032] Example 3, comparative (mixture of dinitriles): [0033] 2 g of catalyst based on Raney nickel comprising 91% by weight of nickel and doped with 2% by weight of Cr are added to 100 g of a 2 0% by weight solution in ethanol of a mixture of dinitriles, referred to as crude MGN, comprising: 86.9% by weight of methylglutaronitrile 11.2% by weight of ethylsuccinonitrile 1.9% by weight of adiponitrile and 1.5 g of NH3 in the form of an aqueous NH4OH solution comprising 2 8% by weight of NH3. The reactor is purged with nitrogen and then with hydrogen. The reaction medium is heated under hydrogen pressure and is stirred when the desired temperature is reached (100°C). The reactor is cooled in order to keep the temperature of the medium at approximately 100°C. The pressure in the reactor is kept constant at a value of 25 bar. When the hydrogen is no longer being consumed, the mark of the end of the reaction, a sample of the reaction medium is withdrawn for analysis by gas chromatography. [0034] The results of analysis show that the conversion of the MGN is 99.9% and the selectivity for MPMD is 22% and that for MPP is 37%. The sum of the selectivities for products of economic value is thus 59%. [0035] Example 4 of the invention (mixture of dinitriles): [0036] 2 g of catalyst based on Raney cobalt comprising 92% by weight of cobalt and doped with 2.2% by weight of Cr and 2.4% by weight of Ni are added to 100 g of a 20% by weight solution in ethanol of a mixture of dinitriles, referred to as crude MGN, comprising: 86.9% by weight of methylglutaronitrile 11.2% by weight of ethylsuccinonitrile 1.9% by weight of adiponitrile and 1.5 g of NH3 in the form of an aqueous NH4OH solution comprising 2 8% by weight of NH3. The reactor is purged with nitrogen and then with hydrogen. The reaction medium is heated under hydrogen pressure and is stirred when the desired temperature is reached (100°C). The reactor is cooled in order to keep the temperature of the medium at approximately 100°C. The pressure in the reactor is kept constant at a value of 25 bar. When the hydrogen is no longer being consumed, the mark of the end of the reaction, a sample of the reaction medium is withdrawn for analysis by gas chromatography. [0037] The results of the analysis show that the MGN is completely converted and the selectivity for MPMD is 58% and that for MPP is 31%. The sum of the selectivities for products of economic value is thus 89%. [0038] Example 5 of the invention (mixture of dinitriles): [0039] 2 g of catalyst based on Raney cobalt comprising 92% by weight of cobalt and doped with 2.2% by weight of Cr and 2.4% by weight of Ni are added to 100 g of a 20% by weight solution in ethanol of a mixture of dinitriles, referred to as crude MGN, comprising: 86.9% by weight of methylglutaronitrile 11.2% by weight of ethylsuccinonitrile 1.9% by weight of adiponitrile and 1.5 g of NH3 in the form of an aqueous NH4OH solution comprising 28% by weight of NH3. The reactor is purged with nitrogen and then with hydrogen. The reaction medium is heated under hydrogen pressure and is stirred when the desired temperature is reached (140°C). The reactor is cooled in order to keep the temperature of the medium at approximately 140°C. The pressure in the reactor is kept constant at a value of 25 bar. When the hydrogen is no longer being consumed, the mark of the end of the reaction, a sample of the reaction medium is withdrawn for analysis by gas chromatography. [0040] The results of the analysis show that the MGN is completely converted and the selectivity for MPMD is 64% and that for MPP is 28%. The sum of the selectivities for products of economic value is thus 92%. [0041] Example 6 of the invention (mixture of dinitriles): [0042] 2 g of catalyst based on Raney cobalt comprising 92% by weight of cobalt and doped with 2.2% by weight of Cr and 2.4% by weight of Ni are added to 100 g of a 20% by weight solution, in an MPP (3-methylpiperidine)/water 95/5 (parts by weight) mixture, of a mixture of dinitriles, referred to as crude MGN, comprising: 86.9% by weight of methylglutaronitrile 11.2% by weight of ethylsuccinonitrile 1.9% by weight of adiponitrile and 1.5 g of NH3 in the form of an aqueous NH4OH solution comprising 2 8% by weight of NH3. The reactor is purged with nitrogen and then with hydrogen. The reaction medium is heated under hydrogen pressure and is stirred when the desired temperature is reached (100°C). The reactor is cooled in order to keep the temperature of the medium at approximately 100°C. The pressure in the reactor is kept constant at a value of 25 bar. When the hydrogen is no longer being consumed, the mark of the end of the reaction, a sample of the reaction medium is withdrawn for analysis by gas chromatography. [0043] The results of the analysis show that the MGN is completely converted and the selectivity for MPMD is 49% and that for MPP is 19%. The sum of the selectivities for products of economic value is thus 68%. [0044] Example 7, comparative (mixture of dinitriles): [0045] 2 g of catalyst based on Raney nickel comprising 91% by weight of nickel and doped with 2% by weight of Cr are added to 100 g of a 20% by weight solution, in an MPP (3-methylpiperidine)/water 95/5 (parts by weight) mixture, of a mixture of dinitriles, referred to as crude MGN, comprising: 86.9% by weight of methylglutaronitrile 11.2% by weight of ethylsuccinonitrile 1.9% by weight of adiponitrile and 1.5 g of NH3 in the form of an aqueous NH4OH solution comprising 2 8% by weight of NH3. The reactor is purged with nitrogen and then with hydrogen. The reaction medium is heated under hydrogen pressure and is stirred when the desired temperature is reached (100°C). The reactor is cooled in order to keep the temperature of the medium at approximately 100°C. The pressure in the reactor is kept constant at a value of 25 bar. When the hydrogen is no longer being consumed, the mark of the end of the reaction, a sample of the reaction medium is withdrawn for analysis by gas chromatography. [0046] The results of the analysis show that the MGN is completely converted and the selectivity for MPMD is 2 0% and that for MPP is 13%. The sum of the selectivities for products of economic value is thus 33%. WHAT IS CLAIMED IS; 1. A process for the manufacture of 2-methylpenta-methylenediamine and 3-methylpiperidine by hydrogenation of methylglutaronitrile, characterized in that the hydrogenation is carried out in the presence of a catalyst comprising cobalt and, as doping elements, nickel and chromium at an absolute hydrogen pressure of less than 50 bar. 2. The process as claimed in claim 1, characterized in that the hydrogenation reaction is carried out under an absolute hydrogen pressure of between 10 and 35 bar. 3. The process as claimed in claim 1 or 2, characterized in that the hydrogenation is carried out in the presence of a solvent chosen from the group consisting of alcohols, water or a mixture of these. 4. The process as claimed in claim 1, 2 or 3, characterized in that the hydrogenation is carried out in the presence of a strong basic inorganic compound chosen from the group consisting of alkali metal hydroxides and ammonium hydroxide. 5. The process as claimed in one of the preceding claims, characterized in that the hydrogenation is carried out at a temperature of between 60 and 160°C. 6. The process as claimed in one of the preceding claims, characterized in that the percentage by weight of cobalt in the catalyst, expressed as Co, is between 85% and 98%, with respect to the weight of catalyst. 7. The process as claimed in one of the preceding claims, characterized in that the percentage by weight of nickel in the catalyst, expressed as Ni, is between 0.1% and 4%, with respect to the weight of catalyst. 8. The process as claimed in one of the preceding claims, characterized in that the percentage by weight of chromium in the catalyst, expressed as Cr, is between 0.1% and 4%, with respect to the weight of catalyst. 9. The process as claimed in one of the preceding claims, characterized in that the cobalt present in the catalyst is a Raney cobalt. 10. The process as claimed in one of the preceding claims, characterized in that a mixture of dinitriles comprising methylglutaronitrile, ethylsuccinonitrile and adiponitrile is introduced into the hydrogenation stage. 11. The process as claimed in claim 10, characterized in that the mixture of dinitriles has the following composition by weight: Methylglutaronitrile : of between 70% and 95% Ethylsuccinonitrile : of between 5% and 30% Adiponitrile : of between 0% and 10%. 12. The process as claimed in either of claims 10 and 11, characterized in that the mixture of dinitriles is enriched in methylglutaronitrile before feeding to the hydrogenation stage.

Full Text

Method for making methylpentamethylenediamine and methylpiperidine

[0001] The present invention relates to a process for the manufacture of 2-methylpentamethylenediamine and of 3-methylpiperidine.

[0002] It relates to a process for the manufacture of 2-methylpentamethylenediamine and 3-methylpiperidine by hydrogenation of methylglutaronitrile.

[0003] Methylglutaronitrile is a compound obtained in conjunction with adiponitrile in the process for the hydrocyanation of butadiene. It is already known to convert this methylglutaronitrile to methylpentamethylenediamine (MPMD) by hydrogenation in the presence of various catalysts, such as Raney cobalt or Raney nickel. High degrees of conversion of methylglutaronitrile to MPMD have been obtained by using pure methylglutaronitrile and by carrying out the hydrogenation under high pressures, as is described in French patents 2 306 202 and 2 306 203.

[0004] A description has also been given of processes for the hydrogenation of methylglutaronitrile to give a mixture of 2-methylpentamethylenediamine (MPMD) and 3-methylpiperidine (MPP) with catalysts based on nickel or Raney nickel under high hydrogen pressures. Such processes have been described in particular in French patents 2 306 204, 2 306 205, 2 306 206, 2 306 207 and 2 306 208. The proportion of MPMD formed with respect to the MPP is variable, depending on the solvent and/or the catalyst used. As for the processes described above, these processes use a pure ethylglutaronitrile (MGN) compound as starting material. A process for the hydrogenation of pure MGN to give MPMD and MPP in the presence of Raney cobalt doped with chromium has also been proposed by patent US 4 885 391. This reaction is advantageously carried out in the presence of water.

The degree of conversion of the MGN to give products of economic value, namely MPMD and MPP, is at most 85%, with formation of approximately 10% of heavy products not of economic value.

[0005] 2-Methylpentamethylenediamine (MPMD) is used mainly in two applications, one as monomer for the manufacture of polyamide, in total or partial replacement of hexamethylenediamine, the other as starting material in the manufacture of β-picoline, which is itself a synthetic intermediate in manufacturing nicotinamide. This process is described in the literature, for example in the paper by S. Lanini and R. Prins published in Appl. Cat. A, 1996, 137, pp 287-306, under the title "Synthesis of 3-picoline from MGN over supported noble metals catalysts".

[0006] The proposal has also been made to synthesize β-picoline by ehydrogenation of a mixture of 2-methyl-pentamethylenediamine and 3-methylpiperidine, as described in patent US 4 401 819.

[0007] Furthermore, methylglutaronitrile is mainly produced in the process for the manufacture of adiponitrile, a synthetic intermediate in the manufacture of hexamethylenediamine and caprolactam, which are important monomers in the production of polyamides.

[0008] Methylglutaronitrile is separated from adiponitrile by distillation and recovered in the form of a distillation fraction. In fact, the fraction recovered is a mixture of dinitrile compounds comprising predominantly methylglutaronitrile and a few percent of ethylsuccinonitrile and of adiponitrile.

[0009] An additional distillation is necessary in order to obtain pure methylglutaronitrile, a product used in the hydrogenation processes of the prior art. The tests described in patent US 4 521 602 show that the conversion of MGN to 3-methylpyridine is obtained with a yield of 80% starting from pure MGN and only 42% with a mixture of dinitriles.

[0010] In addition, the processes for the conversion of MGN to MPMD and MPP described in the literature use high hydrogen pressures in order to obtain a percentage of conversion of MGN to MPMD+MPP of greater than 90%. Hydrogenation reaction is often carried out in the liquid medium.

[0011] In order to make it possible to lower the cost of manufacture of β-picoline, it is important to look for solutions which make it possible to carry out the conversion of MGN either in the pure form or present in the mixture of dinitriles with high yields for conversion of MGN to MPMD and MPP of greater than 90% and under milder operating conditions than those described in the prior art.

[0012] One of the aims of the present invention is to provide a process for the manufacture of 2-methylpenta-methylenediamine and 3-methylpiperidine from pure methylglutaronitrile or methylglutaronitrile as a mixture with other nitriles with high degrees of conversion to MPMD + MPP, these two compounds being of economic value in downstream processes for the manufacture of important chemical compounds, such as (3-picoline, as indicated above.

[9913] To this end, the invention provides a process for the manufacture of 2-methylpentamethylenediamine and 3-methylpiperidine by hydrogenation of methylglutaronitrile, characterized in that the hydrogenation is carried out in the presence of a catalyst comprising cobalt and, as doping elements, chromium and nickel at an absolute hydrogen pressure of less than 50 bar, preferably of less than 40 bar, advantageously of between 10 and 35 bar.

[0014] According to another characteristic of the invention, the hydrogenation is carried out in the presence of a solvent chosen from the group preferably consisting of alcohols, water or a mixture of these. It is also possible to use, as solvent, one of the compounds resulting from the hydrogenation reaction (MPMD and/or MPP), in combination with water.
[0015] Advantageously, the hydrogenation is carried out in the presence of a strong basic inorganic compound chosen from the group consisting of alkali metal hydroxides and ammonium hydroxide. Preferably, the basic compound is potassium hydroxide or aqueous ammonia.
[0016] The hydrogenation can be carried out at a temperature of between 60 and 160°C, advantageously between 80 and 140°C.
[0017] According to a novel characteristic of the invention, the catalyst comprises an amount of cobalt, expressed as elemental Co, of between approximately 85% and approximately 98% of the total weight of the catalyst, an amount of nickel, expressed as elemental Ni, of between approximately 0.1% and approximately 4% by weight of the catalyst and an amount of chromium, expressed as elemental Cr, of between approximately 0.1% and approximately 4% by weight of the catalyst.
[0018] According to a preferred characteristic of the invention, the cobalt present in the catalyst is a Raney cobalt.
[0019] The catalyst of the invention makes it possible to obtain a very high degree of conversion of MGN to MPMD and MPP of approximately 100% and thus to avoid the formation of a large amount of heavy compounds or

compounds having a high boiling point, as was obtained with the catalysts of the state of the art.
[0020] In addition, according to another advantage of the process of the invention using a catalyst with a specific composition, it is possible to use, as starting material to be hydrogenated, a mixture of dinitriles comprising methylglutaronitrile, ethyl-succinonitrile and adiponitrile. This mixture of dinitriles advantageously corresponds to the distillation fraction produced in the process for the manufacture of adiponitrile by double hydrocyanation of butadiene, making it possible to separate the branched dinitriles (methylglutaronitrile, ethylsuccinonitrile) from adiponitrile.
[0021] This mixture of dinitriles generally has the
following composition by weight:
Methylglutaronitrile : of between 70% and 95%
Ethylsuccinonitrile : of between 5% and 30%
Adiponitrile : of between 0% and 10%.
[0022] Thus, the process of the invention makes it possible to obtain a high degree of conversion of the MGN present in this mixture to give MPMD and MPP.
[0023] According to a preferred characteristic of the invention, the mixture of dinitriles can be enriched in methylglutaronitrile before feeding to the hydrogenation stage, for example by distillation.
[0024] 2-Methylpentamethylenediamine, 3-methyl-piperidine or their mixtures can be used as starting materials in the manufacture of β-picoline according to the processes described in the documents already mentioned above.
[0025] In the embodiment of the invention using a mixture of dinitriles as starting materials, it is

possible to use the compounds resulting from the hydrogenation directly in the process for the manufacture of β-picoline, without separation and purification of the MPMD and MPP. However, it may be preferable to carry out a separation of these two compounds from the other products resulting from the hydrogenation of ESN or AdN. This separation can be carried out by any known technique and in particular distillation.
[0026] Other advantages and details of the invention will be illustrated by the examples given below solely by way of illustration.
[0027] Example 1, comparative (pure MGN):
2 g of catalyst based on Raney nickel comprising 91% by weight of nickel and doped with 2% by weight of Cr are added to 100 g of a 20% by weight solution of MGN (99% purity) in ethanol and 1.5 g of NH3 in the form of an aqueous NH4OH solution comprising 28% by weight of NH3. The reactor is purged with nitrogen and then with hydrogen. The reaction medium is heated under hydrogen pressure and is stirred when the desired temperature is reached (100°C). The reactor is cooled in order to keep the temperature of the medium at approximately 100°C. The relative pressure in the reactor is kept constant at a value of 25 bar. When the hydrogen is no longer being consumed, the mark of the end of the reaction, a sample of the reaction medium is withdrawn for analysis by gas chromatography.
[0028] The results of the analysis show that MGN is completely converted and that the selectivity for MPMD is 23% and that for MPP is 44%. The sum of the selectivities for products of economic value is thus 67%.
[0029] Example 2 of the invention (pure MGN):

2 g of catalyst based on Raney cobalt comprising 92% by weight of cobalt and doped with 2.2% by weight of Cr and 2.4% by weight of Ni are added to 100 g of a 20% by weight solution of MGN (99% purity) in ethanol and 1.5 g of NH3 in the form of an aqueous NH4OH solution comprising 2 8% by weight of NH3. The reactor is purged with nitrogen and then with hydrogen. The reaction medium is heated under hydrogen pressure and is stirred when the desired temperature is reached (100°C). The reactor is cooled in order to keep the temperature of the medium at approximately 100°C. The pressure in the reactor is kept constant at a value of 25 bar. When the hydrogen is no longer being consumed, the mark of the end of the reaction, a sample of the reaction medium is withdrawn for analysis by gas chromatography.
[0030] The results of the analysis show that the MGN is completely converted and that the selectivity for MPMD is 80% and that for MPP is 20%. The sum of the selectivities for products of economic value is thus 100%.
[0031] The degree of conversion of the MGN to MPMD and MPP is notably higher than that obtained in example 1 with a catalyst based on Raney nickel but also than that shown in patent US 4 885 391. Specifically, this document describes the hydrogenation of MGN to give MPMD and MPP in the presence of a chromium-doped Raney cobalt catalyst. The maximum degree of conversion is of the order of 80 to 85% with the formation of compounds of high boiling point representing approximately 10% of the products obtained.
[0032] Example 3, comparative (mixture of dinitriles):
[0033] 2 g of catalyst based on Raney nickel comprising 91% by weight of nickel and doped with 2% by weight of Cr are added to 100 g of a 2 0% by weight

solution in ethanol of a mixture of dinitriles, referred to as crude MGN, comprising:
86.9% by weight of methylglutaronitrile 11.2% by weight of ethylsuccinonitrile 1.9% by weight of adiponitrile and 1.5 g of NH3 in the form of an aqueous NH4OH solution comprising 2 8% by weight of NH3. The reactor is purged with nitrogen and then with hydrogen. The reaction medium is heated under hydrogen pressure and is stirred when the desired temperature is reached (100°C). The reactor is cooled in order to keep the temperature of the medium at approximately 100°C. The pressure in the reactor is kept constant at a value of 25 bar. When the hydrogen is no longer being consumed, the mark of the end of the reaction, a sample of the reaction medium is withdrawn for analysis by gas chromatography.
[0034] The results of analysis show that the conversion of the MGN is 99.9% and the selectivity for MPMD is 22% and that for MPP is 37%. The sum of the selectivities for products of economic value is thus 59%.
[0035] Example 4 of the invention (mixture of dinitriles):
[0036] 2 g of catalyst based on Raney cobalt comprising 92% by weight of cobalt and doped with 2.2% by weight of Cr and 2.4% by weight of Ni are added to 100 g of a 20% by weight solution in ethanol of a mixture of dinitriles, referred to as crude MGN, comprising:
86.9% by weight of methylglutaronitrile
11.2% by weight of ethylsuccinonitrile
1.9% by weight of adiponitrile
and 1.5 g of NH3 in the form of an aqueous NH4OH
solution comprising 2 8% by weight of NH3. The reactor is
purged with nitrogen and then with hydrogen. The

reaction medium is heated under hydrogen pressure and is stirred when the desired temperature is reached (100°C). The reactor is cooled in order to keep the temperature of the medium at approximately 100°C. The pressure in the reactor is kept constant at a value of 25 bar. When the hydrogen is no longer being consumed, the mark of the end of the reaction, a sample of the reaction medium is withdrawn for analysis by gas chromatography.
[0037] The results of the analysis show that the MGN is completely converted and the selectivity for MPMD is 58% and that for MPP is 31%. The sum of the selectivities for products of economic value is thus 89%.
[0038] Example 5 of the invention (mixture of dinitriles):
[0039] 2 g of catalyst based on Raney cobalt comprising 92% by weight of cobalt and doped with 2.2% by weight of Cr and 2.4% by weight of Ni are added to 100 g of a 20% by weight solution in ethanol of a mixture of dinitriles, referred to as crude MGN, comprising:
86.9% by weight of methylglutaronitrile 11.2% by weight of ethylsuccinonitrile 1.9% by weight of adiponitrile and 1.5 g of NH3 in the form of an aqueous NH4OH solution comprising 28% by weight of NH3. The reactor is purged with nitrogen and then with hydrogen. The reaction medium is heated under hydrogen pressure and is stirred when the desired temperature is reached (140°C). The reactor is cooled in order to keep the temperature of the medium at approximately 140°C. The pressure in the reactor is kept constant at a value of 25 bar. When the hydrogen is no longer being consumed, the mark of the end of the reaction, a sample of the

reaction medium is withdrawn for analysis by gas chromatography.
[0040] The results of the analysis show that the MGN is completely converted and the selectivity for MPMD is 64% and that for MPP is 28%. The sum of the selectivities for products of economic value is thus 92%.
[0041] Example 6 of the invention (mixture of dinitriles):
[0042] 2 g of catalyst based on Raney cobalt comprising 92% by weight of cobalt and doped with 2.2% by weight of Cr and 2.4% by weight of Ni are added to 100 g of a 20% by weight solution, in an MPP (3-methylpiperidine)/water 95/5 (parts by weight) mixture, of a mixture of dinitriles, referred to as crude MGN, comprising:
86.9% by weight of methylglutaronitrile 11.2% by weight of ethylsuccinonitrile 1.9% by weight of adiponitrile and 1.5 g of NH3 in the form of an aqueous NH4OH solution comprising 2 8% by weight of NH3. The reactor is purged with nitrogen and then with hydrogen. The reaction medium is heated under hydrogen pressure and is stirred when the desired temperature is reached (100°C). The reactor is cooled in order to keep the temperature of the medium at approximately 100°C. The pressure in the reactor is kept constant at a value of 25 bar. When the hydrogen is no longer being consumed, the mark of the end of the reaction, a sample of the reaction medium is withdrawn for analysis by gas chromatography.
[0043] The results of the analysis show that the MGN is completely converted and the selectivity for MPMD is 49% and that for MPP is 19%. The sum of the

selectivities for products of economic value is thus 68%.
[0044] Example 7, comparative (mixture of dinitriles):

[0045] 2 g of catalyst based on Raney nickel comprising 91% by weight of nickel and doped with 2% by weight of Cr are added to 100 g of a 20% by weight solution, in an MPP (3-methylpiperidine)/water 95/5 (parts by weight) mixture, of a mixture of dinitriles, referred to as crude MGN, comprising:

86.9% by weight of methylglutaronitrile

11.2% by weight of ethylsuccinonitrile

1.9% by weight of adiponitrile and

1.5 g of NH3 in the form of an aqueous NH4OH solution comprising 2 8% by weight of NH3. The reactor is purged with nitrogen and then with hydrogen. The reaction medium is heated under hydrogen pressure and is stirred when the desired temperature is reached (100°C). The reactor is cooled in order to keep the temperature of the medium at approximately 100°C. The pressure in the reactor is kept constant at a value of 25 bar. When the hydrogen is no longer being consumed, the mark of the end of the reaction, a sample of the reaction medium is withdrawn for analysis by gas chromatography.

[0046] The results of the analysis show that the MGN is completely converted and the selectivity for MPMD is 2 0% and that for MPP is 13%. The sum of the selectivities for products of economic value is thus 33%.

WHAT IS CLAIMED IS;

1. A process for the manufacture of 2-methylpenta-methylenediamine and 3-methylpiperidine by hydrogenation of methylglutaronitrile, characterized in that the hydrogenation is carried out in the presence of a catalyst comprising cobalt and, as doping elements, nickel and chromium at an absolute hydrogen pressure of less than 50 bar.

2. The process as claimed in claim 1, characterized in that the hydrogenation reaction is carried out under an absolute hydrogen pressure of between 10 and 35 bar.

3. The process as claimed in claim 1 or 2, characterized in that the hydrogenation is carried out in the presence of a solvent chosen from the group consisting of alcohols, water or a mixture of these.

4. The process as claimed in claim 1, 2 or 3, characterized in that the hydrogenation is carried out in the presence of a strong basic inorganic compound chosen from the group consisting of alkali metal hydroxides and ammonium hydroxide.

5. The process as claimed in one of the preceding claims, characterized in that the hydrogenation is carried out at a temperature of between 60 and 160°C.

6. The process as claimed in one of the preceding claims, characterized in that the percentage by weight of cobalt in the catalyst, expressed as Co, is between 85% and 98%, with respect to the weight of catalyst.

7. The process as claimed in one of the preceding claims, characterized in that the percentage by weight of nickel in the catalyst, expressed as Ni, is between 0.1% and 4%, with respect to the weight of catalyst.

8. The process as claimed in one of the preceding claims, characterized in that the percentage by weight of chromium in the catalyst, expressed as Cr, is between 0.1% and 4%, with respect to the weight of catalyst.

9. The process as claimed in one of the preceding claims, characterized in that the cobalt present in the catalyst is a Raney cobalt.

10. The process as claimed in one of the preceding claims, characterized in that a mixture of dinitriles comprising methylglutaronitrile, ethylsuccinonitrile and adiponitrile is introduced into the hydrogenation stage.

11. The process as claimed in claim 10, characterized in that the mixture of dinitriles has the following composition by weight:

Methylglutaronitrile : of between 70% and 95%

Ethylsuccinonitrile : of between 5% and 30%

Adiponitrile : of between 0% and 10%.

12. The process as claimed in either of claims 10 and 11, characterized in that the mixture of dinitriles is enriched in methylglutaronitrile before feeding to the hydrogenation stage.

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Patent Number

278291

Indian Patent Application Number

6159/CHENP/2010

PG Journal Number

53/2016

Publication Date

23-Dec-2016

Grant Date

20-Dec-2016

Date of Filing

29-Sep-2010

Name of Patentee

RHODIA OPERATIONS

Applicant Address

40, RUE DE LA HAIE-COQ, F-93306 AUBERVILLIERS.

Inventors:

#	Inventor's Name	Inventor's Address
1	MARION, PHILIPPE	140, ROUTE DU BUYE, F-69390 VERNAISON.

PCT International Classification Number

C07C209/48, C07C211/09, C07D211/12

PCT International Application Number

PCT/EP09/052966

PCT International Filing date

2009-03-13

PCT Conventions:

#	PCT Application Number	Date of Convention	Priority Country
1	08/01750	2008-03-31	France