CA2050167C - Process for the production of di-(4-aminocyclohexyl)-methane containing 15 to 25% by weight of the trans-trans isomer - Google Patents
Process for the production of di-(4-aminocyclohexyl)-methane containing 15 to 25% by weight of the trans-trans isomer Download PDFInfo
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- CA2050167C CA2050167C CA002050167A CA2050167A CA2050167C CA 2050167 C CA2050167 C CA 2050167C CA 002050167 A CA002050167 A CA 002050167A CA 2050167 A CA2050167 A CA 2050167A CA 2050167 C CA2050167 C CA 2050167C
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
- B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
- B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
- B01J23/46—Ruthenium, rhodium, osmium or iridium
- B01J23/462—Ruthenium
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C209/00—Preparation of compounds containing amino groups bound to a carbon skeleton
- C07C209/68—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton
- C07C209/70—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by reduction of unsaturated amines
- C07C209/72—Preparation of compounds containing amino groups bound to a carbon skeleton from amines, by reactions not involving amino groups, e.g. reduction of unsaturated amines, aromatisation, or substitution of the carbon skeleton by reduction of unsaturated amines by reduction of six-membered aromatic rings
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- C—CHEMISTRY; METALLURGY
- C07—ORGANIC CHEMISTRY
- C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
- C07C2601/00—Systems containing only non-condensed rings
- C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
- C07C2601/14—The ring being saturated
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Abstract
Di-(4-aminocyclohexyl)-methane containing 15 to 25% by weight of the traps-traps isomer can be obtained by the catalytic hydrogenation of di-(4-aminophenyl)-methane at elevated temperature and elevated hydrogen pressure in the presence of a ruthenium-containing supported catalyst containing 0.05 to 5% by weight ruthenium on an Al2 0 3 support which has been treated with compounds of rare earth metals and manganese.
Description
~~:~~~.~i'"d Mo3612 LeA 27,775 PROCESS FOR THE PRODUCTION OF DI-(4-AMINOCYCLOHEXYL)-METHANE
CONTAINING 15 TO 25% BY WEIGHT OF THE TRAMS-TRAMS ISOMER
,~,ACKGROUND OF THE INVENTION
The present invention relates to an improved process for the production of a liquid mixture of the isomers of di-(4-aminocyclohexyl)-methane by hydrogenation of di-(4-aminophenyl)-methane ("MDA"). The liquid isomer mixture obtainable in accordance with the invention contains from 15 to ' 25% by weight and preferably from 18 to 23.5% by weight of the to traps-traps isomer.
A liquid isomer mixture of the type noted above is generally required for the production of an isocyanate derivative which in turn is liquid at room temperature (approximately 10 to 25°C).
i5 In general, the hydrogenation of MDA leads to an isomer mixture in which the cis-cis isomer, the cis-traps isomer and the traps-traps isomer occur together and in which the traps-traps content approaches the equilibrium concentration of around 50% by weight. An isomer composition with the 2o relatively low traps-traps isomer content mentioned above (i.e., from 15 to 25% by weight) can be produced by the complicated conversion process described in German Auslegungschrift 1,593,293. There are other known processes which allow for the preparation of an isomer mixture of 25 di-(4-aminocyclohexyl)-methane containing a specific amount of the traps-traps Isomer (see, e.g., U.S. patents 3,766,272, 3,644,522, 3,155,724, and 3,153,088). European Patent 324,190 describes a hydrogenation process for MDA which produces hydrogenation products wherein the traps-traps content 3o corresponds to the desired value. The process requires the use of special catalysts and the maintenance of certain reaction conditions. However, this process has the disadvantage that the overall yield of di-(4-aminocyclohexyl)-methane is unsatisfactory. In addition, some of the hydrogenation or ~~~~~.~~r conversion processes mentioned must be carried out in the presence of ammonia or high-grade solvents.
Accordingly, the problem addressed by the present invention was to provide a new, simplified and industrially workable process in which the traps-traps isomer content would be in the desired range mentioned above with a high overall conversion. This problem has been solved by the process according to the invention.
DESCRIPTION OF THE INVENTION
zo The present invention is directed to a process for the production of di-(4-aminocyclohexyl)-methane containing from to 25% by weight of the traps-traps isomer by the catalytic hydrogenation of di-(4-aminophenyl)-methane at elevated temperature and elevated hydrogen pressure in the presence of a i5 ruthenium-containing supported catalyst. The process of the invention is characterized by the use of a ruthenium catalyst on an A1203~support which has been treated with compounds of ' rare earth metals and manganese. The ruthenium content of the catalyst used herein is from 0.05 to 5% by weight, preferably 2o from 0.05 to 3% by weight and most preferably from 0.1 to 2% by weight, based on the total weight of the catalyst.
Accordingly, the process of the invention is characterized by the use of a special ruthenium supported catalyst wherein the support, A1203, contains compounds of rare earth metals and z5 manganese. An addition of basic alkali compounds produces further improvements.
The A120a is preferably a- or ~-A1203 and, most preferably, is ~-A1203.
The combined content of rare earth metal and manganese is so from 0.05 to 8% by weight and preferably from 0.2 to 59o by weight, based an the total weight of the catalyst. The weight ratio of rare earth metal to manganese is from 5:1 to 1:5 and preferably from 2:1 to 1:2.
The rare earth metals are the elements of the IIIb group ss of the Periodic system. These include materials such as Mo3612 ~~Si(~~,~~~' scandium, yttrium, lanthanum and the lanthanides. Either one or a mixture of two or more of the rare earth metals may be used. Crude mixtures of rare earth metals of the type which are commercially available and in which only one or two of the s rare earth metals is/are initially enriched can also be used.
It is preferred to use one or more of the elements selected from the group consisting of yttrium, lanthanum, cerium, praseodymium, neodymium and dysprosium. In a particularly preferred embodiment, cerium, lanthanum or a mixture thereof is io used. In an especially preferred embodiment, cerium, which may be in the form of a cerium-enriched mixture, is used. The rare earth metals and manganese are present in the form of their compounds, preferably in oxide form, for treating the A1203 support.
i5 The oxides, hydroxides or carbonates of the alkali metals, preferably NaOH and KOH, may be used as basic additives. The basic additives may be applied to the catalyst support before or after the treatment with the rare earth metals and manganese. The alkali metal addition is preferably between 0.1 2o and l0fo and more preferably between 0.2 to 5%, based on the weight of the catalyst.
The catalyst useable in accordance with the invention may be prepared, for example, by applying compounds of the rare earth metals and manganese to an A1203 in the form of z5 extrudates, pellets or spheres of between about 2 and 10 mm in size. The support thus treated is dried and then further treated with a ruthenium salt, followed by another drying step.
In a preferred embodiment, the catalyst support initially treated with rare earth metals and manganese is heated to a so temperature of 200 to 450'C before the ruthenium is applied.
Compounds of the rare earth metals and manganese may be applied, for example, by impregnation or spraying with suitable salts of the elements mentioned. The salts of the rare earth metals and manganese are converted into compounds which adhere 35 firmly to the catalyst support by a suitable drying temperature Mo3612 iG~~~~.~i~~
CONTAINING 15 TO 25% BY WEIGHT OF THE TRAMS-TRAMS ISOMER
,~,ACKGROUND OF THE INVENTION
The present invention relates to an improved process for the production of a liquid mixture of the isomers of di-(4-aminocyclohexyl)-methane by hydrogenation of di-(4-aminophenyl)-methane ("MDA"). The liquid isomer mixture obtainable in accordance with the invention contains from 15 to ' 25% by weight and preferably from 18 to 23.5% by weight of the to traps-traps isomer.
A liquid isomer mixture of the type noted above is generally required for the production of an isocyanate derivative which in turn is liquid at room temperature (approximately 10 to 25°C).
i5 In general, the hydrogenation of MDA leads to an isomer mixture in which the cis-cis isomer, the cis-traps isomer and the traps-traps isomer occur together and in which the traps-traps content approaches the equilibrium concentration of around 50% by weight. An isomer composition with the 2o relatively low traps-traps isomer content mentioned above (i.e., from 15 to 25% by weight) can be produced by the complicated conversion process described in German Auslegungschrift 1,593,293. There are other known processes which allow for the preparation of an isomer mixture of 25 di-(4-aminocyclohexyl)-methane containing a specific amount of the traps-traps Isomer (see, e.g., U.S. patents 3,766,272, 3,644,522, 3,155,724, and 3,153,088). European Patent 324,190 describes a hydrogenation process for MDA which produces hydrogenation products wherein the traps-traps content 3o corresponds to the desired value. The process requires the use of special catalysts and the maintenance of certain reaction conditions. However, this process has the disadvantage that the overall yield of di-(4-aminocyclohexyl)-methane is unsatisfactory. In addition, some of the hydrogenation or ~~~~~.~~r conversion processes mentioned must be carried out in the presence of ammonia or high-grade solvents.
Accordingly, the problem addressed by the present invention was to provide a new, simplified and industrially workable process in which the traps-traps isomer content would be in the desired range mentioned above with a high overall conversion. This problem has been solved by the process according to the invention.
DESCRIPTION OF THE INVENTION
zo The present invention is directed to a process for the production of di-(4-aminocyclohexyl)-methane containing from to 25% by weight of the traps-traps isomer by the catalytic hydrogenation of di-(4-aminophenyl)-methane at elevated temperature and elevated hydrogen pressure in the presence of a i5 ruthenium-containing supported catalyst. The process of the invention is characterized by the use of a ruthenium catalyst on an A1203~support which has been treated with compounds of ' rare earth metals and manganese. The ruthenium content of the catalyst used herein is from 0.05 to 5% by weight, preferably 2o from 0.05 to 3% by weight and most preferably from 0.1 to 2% by weight, based on the total weight of the catalyst.
Accordingly, the process of the invention is characterized by the use of a special ruthenium supported catalyst wherein the support, A1203, contains compounds of rare earth metals and z5 manganese. An addition of basic alkali compounds produces further improvements.
The A120a is preferably a- or ~-A1203 and, most preferably, is ~-A1203.
The combined content of rare earth metal and manganese is so from 0.05 to 8% by weight and preferably from 0.2 to 59o by weight, based an the total weight of the catalyst. The weight ratio of rare earth metal to manganese is from 5:1 to 1:5 and preferably from 2:1 to 1:2.
The rare earth metals are the elements of the IIIb group ss of the Periodic system. These include materials such as Mo3612 ~~Si(~~,~~~' scandium, yttrium, lanthanum and the lanthanides. Either one or a mixture of two or more of the rare earth metals may be used. Crude mixtures of rare earth metals of the type which are commercially available and in which only one or two of the s rare earth metals is/are initially enriched can also be used.
It is preferred to use one or more of the elements selected from the group consisting of yttrium, lanthanum, cerium, praseodymium, neodymium and dysprosium. In a particularly preferred embodiment, cerium, lanthanum or a mixture thereof is io used. In an especially preferred embodiment, cerium, which may be in the form of a cerium-enriched mixture, is used. The rare earth metals and manganese are present in the form of their compounds, preferably in oxide form, for treating the A1203 support.
i5 The oxides, hydroxides or carbonates of the alkali metals, preferably NaOH and KOH, may be used as basic additives. The basic additives may be applied to the catalyst support before or after the treatment with the rare earth metals and manganese. The alkali metal addition is preferably between 0.1 2o and l0fo and more preferably between 0.2 to 5%, based on the weight of the catalyst.
The catalyst useable in accordance with the invention may be prepared, for example, by applying compounds of the rare earth metals and manganese to an A1203 in the form of z5 extrudates, pellets or spheres of between about 2 and 10 mm in size. The support thus treated is dried and then further treated with a ruthenium salt, followed by another drying step.
In a preferred embodiment, the catalyst support initially treated with rare earth metals and manganese is heated to a so temperature of 200 to 450'C before the ruthenium is applied.
Compounds of the rare earth metals and manganese may be applied, for example, by impregnation or spraying with suitable salts of the elements mentioned. The salts of the rare earth metals and manganese are converted into compounds which adhere 35 firmly to the catalyst support by a suitable drying temperature Mo3612 iG~~~~.~i~~
and, in a preferred embodiment, by heating to between 200 and 450°C. However, compounds of the rare earth metals and manganese may also be applied by co-precipitation of a rare earth metal/manganese hydroxide mixture from rare earth metal and manganese salts onto the impregnated support with alkali hydroxide or ammonia, optionally followed by removal of the soluble components by washing with water. Suitable salts of the rare earth metals and manganese are, in particular, the sulfates, chlorides, acetates and/or nitrates. The support to treated with rare earth metals and manganese is first dried and then heated, preferably for 1 to 120 hours at 200 to 450°C and preferably at 250 to 430°C. The temperature may be increased from lower to higher values within these ranges over the period of time mentioned.
i5 The support thus treated may be subsequently impregnated with ruthenium by applying the ruthenium to the support, for example in the form of an aqueous solution of the chloride, nitrate, acetate or any other suitable salt, by impregnation or spraying, again followed by drying. Before drying, however, 2o the ruthenium-impregnated support may also be treated with a solution of the basic compounds mentioned above, the ruthenium precipitating in the form of the oxide or hydroxide. The water-soluble components may then be removed by washing, followed by drying. Thereafter a catalyst suitable for use in 2s accordance with the invention is available. In a preferred embodiment, however, the catalyst is activated before use, preferably after arrangement in the hydrogenation reactor, by treatment with hydrogen at a temperature in the range from 150 to 350°C. After activation, it may again be desirable to so remove anions, such as chloride, nitrate, acetate or others, and optionally the cations of the basic compounds used for precipitation by washing with water. However, the catalyst support treated with compounds of the rare earth metals and manganese may also first be impregnated with a solution of one 35 of the basic compounds mentioned, and subsequently dried.
Mo3612 2~~~~~~
i5 The support thus treated may be subsequently impregnated with ruthenium by applying the ruthenium to the support, for example in the form of an aqueous solution of the chloride, nitrate, acetate or any other suitable salt, by impregnation or spraying, again followed by drying. Before drying, however, 2o the ruthenium-impregnated support may also be treated with a solution of the basic compounds mentioned above, the ruthenium precipitating in the form of the oxide or hydroxide. The water-soluble components may then be removed by washing, followed by drying. Thereafter a catalyst suitable for use in 2s accordance with the invention is available. In a preferred embodiment, however, the catalyst is activated before use, preferably after arrangement in the hydrogenation reactor, by treatment with hydrogen at a temperature in the range from 150 to 350°C. After activation, it may again be desirable to so remove anions, such as chloride, nitrate, acetate or others, and optionally the cations of the basic compounds used for precipitation by washing with water. However, the catalyst support treated with compounds of the rare earth metals and manganese may also first be impregnated with a solution of one 35 of the basic compounds mentioned, and subsequently dried.
Mo3612 2~~~~~~
Solutions of ruthenium salts may then be applied to the basified catalyst support, the ruthenium being precipitated in the form of its oxide or hydroxide at the moment of impregnation. In this case, too, the catalyst is ready for use s after drying, although it is preferably first activated with hydrogen in the manner described above. In this variant, too, the ruthenium supported catalyst is ready for use despite the presence of the residues of such alkaline compounds. In a preferred embodiment, however, it is washed with water as io described above.
The application of the various substances to the A1203 support by impregnation or spraying and the apparatus required for this purpose are known in the art. It is also known that the required degree of application can be adjusted through the ~5 choice of the quantity and concentration of the solutions of the elements mentioned.
The hydrogenation reaction according to the invention takes place at a temperature in the range from 80 to 160°C and preferably at a temperature in the range from 90 to 140°C. The 2o choice of the temperature is determined by the required reaction rate and also by the desired composition of the isomer mixture. The reaction rate increases with increasing temperature, as does the traps-traps content of the isomer mixture formed. The catalyst has an isomerizing effect on the 2s hydrogenation product, particularly at relatively high temperatures, so that the traps-traps content can increase even further in the event of prolonged contact. Accordingly, it is generally preferable to remove the hydrogenation product from the catalyst after the uptake of hydrogen has stopped.
so According to the invention, the hydrogen pressure applied is in the range from 20 to 500 bar and preferably in the range from 200 to 400 bar. The higher the hydrogen pressure, the faster the hydrogenation reaction. By applying a relatively high hydrogen pressure, therefore, it is possible to keep to a 35 relatively low hydrogenation temperature and/or a relatively Mo3612 ~~~~~~
The application of the various substances to the A1203 support by impregnation or spraying and the apparatus required for this purpose are known in the art. It is also known that the required degree of application can be adjusted through the ~5 choice of the quantity and concentration of the solutions of the elements mentioned.
The hydrogenation reaction according to the invention takes place at a temperature in the range from 80 to 160°C and preferably at a temperature in the range from 90 to 140°C. The 2o choice of the temperature is determined by the required reaction rate and also by the desired composition of the isomer mixture. The reaction rate increases with increasing temperature, as does the traps-traps content of the isomer mixture formed. The catalyst has an isomerizing effect on the 2s hydrogenation product, particularly at relatively high temperatures, so that the traps-traps content can increase even further in the event of prolonged contact. Accordingly, it is generally preferable to remove the hydrogenation product from the catalyst after the uptake of hydrogen has stopped.
so According to the invention, the hydrogen pressure applied is in the range from 20 to 500 bar and preferably in the range from 200 to 400 bar. The higher the hydrogen pressure, the faster the hydrogenation reaction. By applying a relatively high hydrogen pressure, therefore, it is possible to keep to a 35 relatively low hydrogenation temperature and/or a relatively Mo3612 ~~~~~~
short contact time with the catalyst in order to reduce the traps-traps content of the hydrogenation product.
Where hydrogenation is carried out discontinuously in an autoclave, the course of the reaction can be followed and, s thus, the end of the hydrogenation time can be determined from the amount of hydrogen taken up. The hydrogenation time is generally between 2 and 5 hours, depending on the quantity of catalyst and the temperature applied.
In a particularly advantageous embodiment, the process is io . conducted continuously. The catalyst can be introduced in the form of granules into a vertical pressure tube. The MDA to be hydrogenated, optionally together with an inert solvent for dilution, and the hydrogen are passed through the catalyst bed from above. The hydrogen removed from the reaction product discharged may be reused for the reaction. Under given reaction conditions, the most favorable throughput rate can be established and followed by gas-chromatographic analysis ("GC"
analysis) of the hydrogenation product. A catalyst load of 0.05 to 0.5 kg MDA per liter catalyst per hour has proven to be 2o particularly advantageous.
Suitable inert diluents are liquid compounds, such as dioxane, tetrahydrofuran, isobutanol or tert-butanol, which are known to the art as being inert to hydrogenation. In a preferred embodiment, however, part of the hydrogenation 25 product may be used for dilution, eliminating the need to introduce a diluent from outside the system. Where an inert diluent/solvent or the hydrogenation product formed is used for dilution, the weight ratio of MDA to diluent is generally from 1:0.2 to 1:2 and preferably from 1:0.5 to 1:1.
so Compared with known processes, the process according to the invention has the advantage of a higher yield in conjunction with the direct establishment of the desired isomer ratio and the use of a ruthenium catalyst which is easy to produce.
s5 In the following Examples, all percentages are by weight.
Mo3612 EXAMPLES
Examgle 1 200 g of a commercially available ~-A1203 having a specific surface of 350 m2/g and a bead diameter of 2 to 6 mm s were impregnated with a solution which had been prepared from 12.4 g Ce(N03)3 ' 6H20, 18.28 g Mn(N03)2 ' 4H20 and 50 g water.
The impregnated A1203 was dried for 18 hours at 120°C in a water jet vacuum and then heated for 3 hours at 400°C. The catalyst support thus produced was impregnated with 70 g of an to aqueous RuCl3 solution containing 2 g Ru. The moist catalyst was dried for 18 hours at 120°C in a water jet vacuum and activated for 3 hours at 350°C in a stream of hydrogen (100 liters H2/hour).
ExamPl e~
is 25 ml (19 g) of the Ru-Ce-Mn-A1203 catalyst prepared in accordance with Example 1 containing 1% Ru, 2fo Ce and 2% Mn were used for the hydrogenation of di-(4-aminophenyl)-methane .(MDA) in a 0.25 liter shaker autoclave. A sieve basket filled with the catalyst was arranged inside the autoclave. 40 g MDA
2o dissolved in 40 g tert-butanol were hydrogenated six times in succession with this catalyst filling. The hydrogen pressure was 260 to 300 bar and the reaction temperature was 140°C. The necessary hydrogenation time was between 240 and 300 minutes.
After each hydrogenation, the autoclave was cooled to room 2s temperature; the reaction product was removed and the autoclave was refilled with a solution of MDA in tert-butanol. The reaction products were analyzed for their content of traps-traps isomer and di-(4-aminocyclohexyl)-methane ("HMDA").
The results obtained are shown in the following Table (the so amount of traps-traps isomer is based on the amount of the HMDA):
Mo3612 2~~~~~~
_8_ Hydrogenation Trans-trans 3- and 4-Nuclear HMDA
time (rains.) isomer (%) compounds (%) (%) 300 22.5 2.8 96.5 s 265 19.8 2.6 96.9 240 19.0 1.7 97.9 270 21.0 1.5 98.3 260 20.6 1.9 97.7 Example 3 io 150 g of the catalyst prepared in accordance with Example l were aftertreated by impregnation with a solution which had been prepared from 54 g water and 6 g NaOH. The quantity of sodium hydroxide used corresponded to the absorption capacity of the catalyst. The impregnated catalyst was dried for 20 15 hours at 100°C. 60 ml (53 g) of the catalyst thus produced were arranged in a vertical pressure tube (diameter 14 mm, . length 70 cm) which was heated by an oil thermostat. The spaces in the catalyst layer were filled with fine sea sand (0.2 to 0.3 mm).
2o A mixture of 1 part by weight MDA and 1 part by weight tert-butanol was introduced onto the catalyst from above together with hydrogen at 270 bar/112°C. The liquid trickled downwards through the catalyst into a separator. 30 to 50 liters hydrogen/hour were removed at the head of the separator.
2s The MDA throughput corresponded to a catalyst load of 0.11 to ' 0.13 g MDA/ml cat. per hour and was kept in this range.
After 333 hours, the reaction product had the following camposition according to analysis by gas chromatography:
Trans-trans isomer: 18.2%
30 . 3- and 4-nuclear compounds: 0.25%
Di-(4-aminocyclohexyl)-methane 98.9%
Secondary products 0.85%
Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be Mo3612 _g_ 2~~~~.~ d understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
Mo3612
Where hydrogenation is carried out discontinuously in an autoclave, the course of the reaction can be followed and, s thus, the end of the hydrogenation time can be determined from the amount of hydrogen taken up. The hydrogenation time is generally between 2 and 5 hours, depending on the quantity of catalyst and the temperature applied.
In a particularly advantageous embodiment, the process is io . conducted continuously. The catalyst can be introduced in the form of granules into a vertical pressure tube. The MDA to be hydrogenated, optionally together with an inert solvent for dilution, and the hydrogen are passed through the catalyst bed from above. The hydrogen removed from the reaction product discharged may be reused for the reaction. Under given reaction conditions, the most favorable throughput rate can be established and followed by gas-chromatographic analysis ("GC"
analysis) of the hydrogenation product. A catalyst load of 0.05 to 0.5 kg MDA per liter catalyst per hour has proven to be 2o particularly advantageous.
Suitable inert diluents are liquid compounds, such as dioxane, tetrahydrofuran, isobutanol or tert-butanol, which are known to the art as being inert to hydrogenation. In a preferred embodiment, however, part of the hydrogenation 25 product may be used for dilution, eliminating the need to introduce a diluent from outside the system. Where an inert diluent/solvent or the hydrogenation product formed is used for dilution, the weight ratio of MDA to diluent is generally from 1:0.2 to 1:2 and preferably from 1:0.5 to 1:1.
so Compared with known processes, the process according to the invention has the advantage of a higher yield in conjunction with the direct establishment of the desired isomer ratio and the use of a ruthenium catalyst which is easy to produce.
s5 In the following Examples, all percentages are by weight.
Mo3612 EXAMPLES
Examgle 1 200 g of a commercially available ~-A1203 having a specific surface of 350 m2/g and a bead diameter of 2 to 6 mm s were impregnated with a solution which had been prepared from 12.4 g Ce(N03)3 ' 6H20, 18.28 g Mn(N03)2 ' 4H20 and 50 g water.
The impregnated A1203 was dried for 18 hours at 120°C in a water jet vacuum and then heated for 3 hours at 400°C. The catalyst support thus produced was impregnated with 70 g of an to aqueous RuCl3 solution containing 2 g Ru. The moist catalyst was dried for 18 hours at 120°C in a water jet vacuum and activated for 3 hours at 350°C in a stream of hydrogen (100 liters H2/hour).
ExamPl e~
is 25 ml (19 g) of the Ru-Ce-Mn-A1203 catalyst prepared in accordance with Example 1 containing 1% Ru, 2fo Ce and 2% Mn were used for the hydrogenation of di-(4-aminophenyl)-methane .(MDA) in a 0.25 liter shaker autoclave. A sieve basket filled with the catalyst was arranged inside the autoclave. 40 g MDA
2o dissolved in 40 g tert-butanol were hydrogenated six times in succession with this catalyst filling. The hydrogen pressure was 260 to 300 bar and the reaction temperature was 140°C. The necessary hydrogenation time was between 240 and 300 minutes.
After each hydrogenation, the autoclave was cooled to room 2s temperature; the reaction product was removed and the autoclave was refilled with a solution of MDA in tert-butanol. The reaction products were analyzed for their content of traps-traps isomer and di-(4-aminocyclohexyl)-methane ("HMDA").
The results obtained are shown in the following Table (the so amount of traps-traps isomer is based on the amount of the HMDA):
Mo3612 2~~~~~~
_8_ Hydrogenation Trans-trans 3- and 4-Nuclear HMDA
time (rains.) isomer (%) compounds (%) (%) 300 22.5 2.8 96.5 s 265 19.8 2.6 96.9 240 19.0 1.7 97.9 270 21.0 1.5 98.3 260 20.6 1.9 97.7 Example 3 io 150 g of the catalyst prepared in accordance with Example l were aftertreated by impregnation with a solution which had been prepared from 54 g water and 6 g NaOH. The quantity of sodium hydroxide used corresponded to the absorption capacity of the catalyst. The impregnated catalyst was dried for 20 15 hours at 100°C. 60 ml (53 g) of the catalyst thus produced were arranged in a vertical pressure tube (diameter 14 mm, . length 70 cm) which was heated by an oil thermostat. The spaces in the catalyst layer were filled with fine sea sand (0.2 to 0.3 mm).
2o A mixture of 1 part by weight MDA and 1 part by weight tert-butanol was introduced onto the catalyst from above together with hydrogen at 270 bar/112°C. The liquid trickled downwards through the catalyst into a separator. 30 to 50 liters hydrogen/hour were removed at the head of the separator.
2s The MDA throughput corresponded to a catalyst load of 0.11 to ' 0.13 g MDA/ml cat. per hour and was kept in this range.
After 333 hours, the reaction product had the following camposition according to analysis by gas chromatography:
Trans-trans isomer: 18.2%
30 . 3- and 4-nuclear compounds: 0.25%
Di-(4-aminocyclohexyl)-methane 98.9%
Secondary products 0.85%
Although the invention has been described in detail in the foregoing for the purpose of illustration, it is to be Mo3612 _g_ 2~~~~.~ d understood that such detail is solely for that purpose and that variations can be made therein by those skilled in the art without departing from the spirit and scope of the invention except as it may be limited by the claims.
Mo3612
Claims (13)
1. In a process for the production of di-(4-aminocyclohexyl)-methane containing 15 to 25% by weight of the traps-traps isomer comprising catalytically hydrogenating di-(4-aminophenyl)-methane at a temperature in the range of 80° to 160°C. and hydrogen pressure in the range of from 20 to 500 bar in the presence of a catalyst, the improvement wherein said catalyst is a ruthenium catalyst on an Al2O3 support which has been treated with compounds of rare earth metals and manganese in a weight ratio of rare earth metal to manganese of from 5:1 to 1:5 and in a combined content of rare earth metal and manganese of from 0.05 to 8% by weight, the ruthenium content of said catalyst being from 0.05 to 5% by weight, based on the total weight of said catalyst.
2. The process of Claim 1, wherein the ruthenium content is from 0.05 to 3% by weight.
3. The process of Claim 2, wherein the ruthenium content is from 0.1 to 2% by weight.
4. The process of Claim 1, wherein said combined content is from 0.2 to 5% by weight and said ratio is from 2:1 to 1:2.
5. The process of Claim 1, wherein the treated catalyst support is heated to a temperature of from 200° to 450°C. and the ruthenium is subsequently applied.
6. The process of Claim 5, wherein the treated catalyst support is heated to a temperature of from 250° to 430°C.
7. The process of Claim 1, wherein the rare earth metal is one or more elements selected from the group consisting of yttrium, lanthanum, cerium, praseodymium, neodymium and dysprosium.
8. The process of Claim 7, wherein the rare earth metal is cerium and/or lanthanum.
9. The process of Claim 1, wherein the catalyst contains an oxide, hydroxide or carbonate of an alkali metal.
10. The process of Claim 1, wherein the Al2O3 is used in .alpha.- or .gamma.-Al2O3.
11. The process of Claim 1, wherein, before the hydrogenation of di-(4-aminophenyl)-methane, the catalyst is activated by treatment with hydrogen at 150° to 350°C.
12. The process of Claim 1, wherein the reaction is carried out continuously, and a catalyst load of 0.05 to 0.5 kg di-(4-aminophenyl) methane per liter catalyst per hour is maintained.
13. The process of Claim 1, wherein the di-(4-aminophenyl)-methane to be hydrogenated is used in admixture with a solvent/diluent in a weight ratio of from 1:0.2 to 1:2, and the solvent/diluent used is selected from the group consisting of dioxane, tetrahydrofuran, isobutanol, tert-butanol or the hydrogenation mixture formed.
Applications Claiming Priority (2)
| Application Number | Priority Date | Filing Date | Title |
|---|---|---|---|
| DEP4028270.8 | 1990-09-06 | ||
| DE4028270A DE4028270A1 (en) | 1990-09-06 | 1990-09-06 | PROCESS FOR THE PREPARATION OF DI- (4-AMINOCYCLOHEXYL) -METHANE WITH A SHARE OF 15 TO 25% BY WEIGHT OF THE TRANS-TRANS ISOMER |
Publications (2)
| Publication Number | Publication Date |
|---|---|
| CA2050167A1 CA2050167A1 (en) | 1992-03-07 |
| CA2050167C true CA2050167C (en) | 2001-04-17 |
Family
ID=6413715
Family Applications (1)
| Application Number | Title | Priority Date | Filing Date |
|---|---|---|---|
| CA002050167A Expired - Fee Related CA2050167C (en) | 1990-09-06 | 1991-08-30 | Process for the production of di-(4-aminocyclohexyl)-methane containing 15 to 25% by weight of the trans-trans isomer |
Country Status (4)
| Country | Link |
|---|---|
| EP (1) | EP0476359B1 (en) |
| JP (1) | JP3046862B2 (en) |
| CA (1) | CA2050167C (en) |
| DE (2) | DE4028270A1 (en) |
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10294194B2 (en) | 2015-03-09 | 2019-05-21 | Mitsubishi Gas Chemical Company, Inc. | Isomerization method for diaminodicyclohexylmethane |
Families Citing this family (3)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| DE4328007A1 (en) * | 1993-08-20 | 1995-02-23 | Huels Chemische Werke Ag | Catalyst for the production of bis-para-aminocyclohexylmethane with a low proportion of trans-trans isomer by hydrogenation of methylenediamine |
| DE4404220A1 (en) * | 1994-02-10 | 1995-08-17 | Bayer Ag | Ruthenium catalysts, their production and a process for the preparation of cycloaliphatic polyamines using these catalysts |
| DE10231119A1 (en) * | 2002-07-10 | 2004-02-05 | Degussa Ag | Process for increasing the selectivity of the hydrogenation of 4,4'-diaminodiphenylmethane to 4,4'-diaminodicyclohexylmethane in the presence of an N-alkyl-4,4'-diaminodiphenylmethane |
Family Cites Families (6)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US3404098A (en) * | 1965-12-23 | 1968-10-01 | Du Pont | Platinum group metal catalysts supported on rare earth carbonates |
| CH515882A (en) * | 1965-12-23 | 1971-11-30 | Du Pont | 4,4'-Methylene di-(cyclohexylamine) prepn - with control of stereoisomer concn |
| US3644522A (en) * | 1969-04-04 | 1972-02-22 | Du Pont | Catalytic hydrogenation of nitrogen containing compounds over supported ruthenium catalysts |
| DE3045719A1 (en) * | 1980-12-04 | 1982-07-08 | Basf Ag, 6700 Ludwigshafen | METHOD FOR PRODUCING CYCLOALIPHATIC AND / OR AROMATIC AMINES |
| EP0324190B1 (en) * | 1988-01-14 | 1993-05-12 | Hüls Aktiengesellschaft | Process for the production of 4,4'-diamino-dicyclohexylmethane with a low trans-trans isomer content by the catalytic hydrogenation of 4,4'-diaminodiphenylmethane |
| DE3824822A1 (en) * | 1988-07-21 | 1990-01-25 | Bayer Ag | RUTHENIUM CARRIER CATALYST, ITS PRODUCTION AND ITS USE IN THE PRODUCTION OF CYCLOHEXYLAMINE SUBSTITUTEDLY, AND SUBSTITUTED DICYCLOHEXYLAMINE SUBSTITUTED, IF ANY |
-
1990
- 1990-09-06 DE DE4028270A patent/DE4028270A1/en not_active Withdrawn
-
1991
- 1991-08-24 DE DE91114225T patent/DE59100432D1/en not_active Expired - Fee Related
- 1991-08-24 EP EP91114225A patent/EP0476359B1/en not_active Expired - Lifetime
- 1991-08-30 JP JP3244857A patent/JP3046862B2/en not_active Expired - Fee Related
- 1991-08-30 CA CA002050167A patent/CA2050167C/en not_active Expired - Fee Related
Cited By (1)
| Publication number | Priority date | Publication date | Assignee | Title |
|---|---|---|---|---|
| US10294194B2 (en) | 2015-03-09 | 2019-05-21 | Mitsubishi Gas Chemical Company, Inc. | Isomerization method for diaminodicyclohexylmethane |
Also Published As
| Publication number | Publication date |
|---|---|
| EP0476359B1 (en) | 1993-09-29 |
| JP3046862B2 (en) | 2000-05-29 |
| DE4028270A1 (en) | 1992-03-12 |
| JPH04247056A (en) | 1992-09-03 |
| DE59100432D1 (en) | 1993-11-04 |
| CA2050167A1 (en) | 1992-03-07 |
| EP0476359A1 (en) | 1992-03-25 |
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