JPH0825966B2 - Process for producing 3-aminomethyl-3,5,5-trimethylcyclohexylamine - Google Patents

Description

Detailed Description of the Invention

[0001]

The present invention relates to 3-aminomethyl-3,
The present invention relates to a method for producing 5,5-trimethylcyclohexylamine. More specifically, 3-cyano-3,5,5
-Improving a method for producing 3-aminomethyl-3,5,5-trimethylcyclohexylamine from trimethylcyclohexanone, ammonia and hydrogen.

[0002]

2. Description of the Related Art 3-Aminomethyl-3,
5,5-trimethylcyclohexylamine (hereinafter IP
It may be abbreviated as DA. ) Is produced using a metal cobalt-supported silica catalyst, 3-cyano-3,5,5-
3-Aminomethyl-3,5,5-trimethylcyclohexylamine and 3-aminomethyl-3,5,5-trimethylcyclohexanol (isophorone) from trimethylcyclohexanone (hereinafter sometimes abbreviated as CIP), ammonia and hydrogen. Amino alcohol, hereafter IPA
It may be abbreviated as A. ) Is manufactured by Japanese Patent Publication No. 39-109
No. 23 is disclosed.

In the above publication, a metal cobalt-supported silica catalyst prepared by crushing is used, and reaction conditions include (1) ammonia content in a charged mixture, (2) reaction temperature,
And (3) studying hydrogen pressure. Regarding ammonia of (1), when the content of ammonia decreases, the reaction proceeds to the isophorone aminoalcohol side, and the content increases, and 3-aminomethyl-3,5 , 5-trimethylcyclohexylamine side reaction, and the ratio suitable for the production of 3-aminomethyl-3,5,5-trimethylcyclohexylamine is 3 to 10 mol of ammonia /
The ratio suitable for the formation of CIP moles and 3-aminomethyl-3,5,5-trimethylcyclohexylamine is 10 to 30 moles ammonia / CIP moles. Regarding the reaction temperature of the above (2), the optimum temperature Is 50-150
Regarding the hydrogen pressure in (3) above, the hydrogen pressure does not fall below 50 atm. However, the method disclosed in Japanese Examined Patent Publication No. 39-10923 has a problem that must be solved as an industrial production method of 3-aminomethyl-3,5,5-trimethylcyclohexylamine. That is,

Since crushed particles are used as the catalyst, the shape of the catalyst is not constant, and during the reaction, the particles are abraded and pulverized, and the particle size distribution shifts toward a very small average particle size, which reduces the catalytic activity. , The selectivity is deteriorated, and the by-product 1,3,3-trimethyl-6-azabicyclo [3.2.
1] A large amount of octane (hereinafter sometimes abbreviated as TMAB) is generated,

It is uneconomical in terms of recovery and reuse of ammonia because a large amount of ammonia is used with respect to 3-cyano-3,5,5-trimethylcyclohexanone,

The hydrogen pressure is described as 50 atm or higher, and at low pressure, CIP generates hydrogen cyanide,
Since the yield of 3-aminomethyl-3,5,5-trimethylcyclohexylamine is lowered, generation of hydrogen cyanide is suppressed in the Examples, and 3-aminomethyl-3,3
To obtain 5,5-trimethylcyclohexylamine 1
Adopting a high hydrogen pressure condition of 40 to 150 atm, and hydrogen cyanide poisoning the catalyst,

Since a crushed catalyst is used, the catalyst is abraded and pulverized during the reaction, and the particle size distribution shifts to a smaller average particle size, the sedimentation property of the catalyst deteriorates, and separation from the reaction liquid is difficult. To be

The crushed catalyst is sieved to narrow the particle size distribution, and even when a catalyst having a relatively large average particle size is used, the particle size distribution is widened due to abrasion and pulverization during the reaction.
There is a problem as an industrial production method in that the average particle diameter becomes considerably small and it becomes difficult to separate the catalyst from the reaction solution.

In particular, the activity associated with atomization of the above catalyst,
The deterioration of selectivity and the high-pressure hydrogen pressure condition greatly affect productivity in terms of catalytic reactivity (catalytic activity, selectivity and reaction yield), catalyst cost and operability. For example, in a continuous reaction, if the selectivity is poor, the amount of by-products is increased, the separation and purification of the by-product becomes difficult, the reaction yield is reduced, and the catalyst is pulverized to reduce the activity, resulting in a reaction loss. The problem is that it is necessary to replenish the catalyst frequently or to replenish a large amount of the catalyst due to the decrease in the rate, and the reaction yield decreases when the pressure is lowered, and the catalyst is poisoned by hydrogen cyanide. This is a problem that must be addressed.

Further, regarding the above-mentioned large amount of ammonia used, deterioration of the catalyst settling property due to atomization, and spread of the particle size distribution of the catalyst during use, reaction equipment (ammonia recovery equipment, catalyst filtration equipment) ) And operability have a great impact on productivity. For example, the equipment for recovering excess ammonia becomes too large, and the equipment cost increases. As a method of recovering and reusing the catalyst, when filtering with a filter, if the average particle size of the catalyst is very small, the catalyst will pass through the filter and complete filtration will not be possible. It must be filtered or the filter mesh must be fine. However, if the mesh of the filter is made fine, the filtration time becomes longer, the filter gradually becomes clogged, and eventually the filtration becomes impossible, and it is necessary to frequently replace the filter. Is.

Even when the catalyst is allowed to settle to remove the supernatant of the reaction solution and the catalyst is reused, if the average particle size of the catalyst is small, the sedimentation rate of the catalyst becomes slow and the catalyst floats in the reaction solution for a long time. Therefore, the amount of supernatant collected from the reaction mixture will decrease,
Productivity is very poor.

Therefore, an object of the present invention is to provide 3-aminomethyl-3,5,5-trimethylcyclohexylamine with
3-Cyano-3,5,5 using a metallic cobalt-based supported catalyst
In the method for producing 3-aminomethyl-3,5,5-trimethylcyclohexylamine from 5-trimethylcyclohexanone, ammonia and hydrogen, solving the problem caused by using the granular catalyst by the above-mentioned crushing, namely, To provide a production method that prevents deterioration and improve selectivity and reaction rate, provide a production method that facilitates catalyst recovery and reuse, and provides a production method that can reduce the amount of ammonia used. is there.

[0013]

As a result of intensive studies in view of the above problems, the present inventors have found that the above problems can be solved by using silica or silica-alumina fine spherical catalysts carrying metallic cobalt. Heading The invention has been reached. That is, the present invention relates to 3-cyano-3,5,5
A method for producing 3-aminomethyl-3,5,5-trimethylcyclohexylamine by reacting trimethylcyclohexanone with ammonia and hydrogen in the presence or absence of an organic solvent, wherein silica or silica carrying metallic cobalt- The present invention provides a method for producing 3-aminomethyl-3,5,5-trimethylcyclohexylamine, which is characterized by using an alumina fine spherical catalyst.

The present invention will be described in detail below. In the present invention, a spherical catalyst is a catalyst in which 90% or more of the projections are substantially circular at any angle of projection, and examples thereof include an elliptical shape, a cylindrical shape, a conical shape, a rugby ball shape, and the like. , The content of particles having acute and obtuse angles is 10
% Or less of the catalyst.

In the method of the present invention, since a spherical catalyst having a substantially constant shape is used, changes in particle size distribution and average particle size during the reaction are reduced. Therefore, for example, the reaction activity and selectivity are high, the decrease in the reaction activity and selectivity of the catalyst due to repeated use is small, the ammonia mole / CIP mole ratio can be lowered, and the ammonia can be easily recovered. When the catalyst is recovered and reused, it is filtered off because the catalyst activity is high under low hydrogen pressure, the poisoning of the catalyst is small, the catalyst is not abraded during the reaction, the powder is less pulverized and the sedimentation of the catalyst is good. It has the advantage of improving productivity such as easy collection.

[0016]

[Method for producing fine spherical catalyst] The fine spherical catalyst used in the method of the present invention is silica or silica-alumina catalyst carrying metallic cobalt. Such a fine spherical catalyst can be prepared, for example, by the following method. That is, as a metal cobalt source, cobalt chloride, cobalt nitrate, cobalt sulfate, cobalt phosphate, cobalt carbonate, cobalt acetate, cobalt oxalate, cobalt formate, cobalt hydroxide, etc. are used, and the metal cobalt source and silica sol (or silica-alumina sol) are used. ) And mix well,
A silica fine particle spherical gel (or silica-alumina) carrying 10 to 60% by weight of cobalt ions is obtained by spray-drying a slurry of 5 to 40% by weight obtained by coprecipitation with an alkali such as an aqueous solution of sodium hydroxide and an aqueous solution of sodium carbonate. A fine spherical gel) is prepared.

Alternatively, silica sol (or silica-
Alumina sol) is finely-divided into spherical silica gel (or silica
An alumina fine particle spherical gel is impregnated with the aqueous solution of the cobalt source to prepare a silica fine particle spherical gel (or silica-alumina fine particle spherical gel) carrying 10 to 40% by weight of cobalt ions. Next, after the silica fine spherical gel supporting cobalt ions (or silica-alumina fine spherical spherical gel) is calcined at a temperature of about 300 ° C. under a stream of air and nitrogen, hydrogen reduction is performed at a temperature of about 350 ° C. It is possible to obtain a silica fine spherical catalyst (or silica-alumina fine spherical catalyst) supporting cobalt.

In the present invention, the fine spherical catalyst may have a particle size distribution of 2 to 500 μm, preferably a particle size distribution of 40 to 350 μm, and an average particle size of 100 to 150 μm. Is. If the particle size distribution is narrow, the reaction activity decreases, so a broad particle size distribution is preferable. However, even though the particle size distribution is wide, a catalyst having a small average particle size is uneconomical because it takes a long time to separate from the reaction solution after the reaction, and a catalyst having a large average particle size even if the particle size distribution is wide is considered as a reaction solution. However, the above range is preferable because the dispersibility of the catalyst during the reaction is deteriorated and the reaction yield is reduced although

The spheroidizing of the catalyst is carried out by a spray drying method. That is, a slurry of cobalt ion-supporting silica sol (or cobalt ion-supporting silica-alumina sol) or silica sol (or silica-alumina sol)
Of an aqueous solution of sodium hydroxide and an aqueous solution of sodium carbonate which has a concentration of 10 to 10%.
It is carried out by a method of spray-drying 60% at 100 to 150 ° C.

The spray drying method is a drying method in which a liquid or mud-like material is spray-dispersed in hot air and rapidly dried while being conveyed by hot air to obtain a powdery product. The feature of this drying method is that the product is obtained in the form of hollow or solid spherical particles.

As a method of atomizing the material, a method of supplying the material onto a high-speed rotating disk and scattering and atomizing it by centrifugal force (a disk type method), and a method of pressurizing the material and ejecting it from an orifice of a nozzle ( Nozzle type method),
A method of spraying a material at a low pressure on the principle of atomization by a jet of compressed air, steam or an inert gas is used. In the disk type method, the diameter of the high speed rotating disk is usually 10 to 35 cm, and the rotation speed is 3000 to 15000 rp.
The nozzle diameter of the pressure nozzle type is 0.3 to 5 mm, and the pressure is 20 to 700.
It is about Kg / cm ² . The pressure of the compressed gas in the two-fluid nozzle type is ^{2 to} 8 kg / cm ² , and the pressure of the material fluid is 1 to 5
It is about Kg / cm ² . Generally, the hot air temperature is 150 to 550 ° C., the spray particle size range is 2 to 500 μm, and the drying time is about 5 to 20 seconds.

The cobalt-based catalyst used in the present invention is finely pulverized by any method and combined with a spray-drying method to form fine spheres. Average particle size of 100 μm or more,
In order to have a narrow particle size distribution and a high dry yield, it is preferable to use a disk type method for atomization. The shape and rotation number of the disk, the physical properties of the slurry, particularly the slurry concentration, viscosity, specific gravity, etc. are the main factors that determine the quality of the spherical shape of the product in the combination of the disk type method and spray drying, and the particle size distribution.

In the case of the catalyst of the present invention, the cobalt ion-supporting silica sol obtained by the coprecipitation method (or cobalt ion-supporting silica-alumina sol) is rotated at a disk rotation speed of 8000 to 10
000 rpm, slurry concentration 15-30% by weight, viscosity 0.5
By spray-drying in the range of 4 poises, fine spherical particles can be obtained as a product. The shape of the disc is
Various types such as Ben, Kessner, and pin type are known, but from the viewpoint of sharpening the particle size distribution, the use of pin type disks gives favorable results.

[0024]

[Reaction Conditions] The reaction of the present invention is carried out by a continuous reaction by a catalyst suspension, a catalyst flow and a catalyst fixing system. The catalyst can be used in an amount of 0.02 equivalent or more with respect to 3-cyano-3,5,5-trimethylcyclohexanone, but from the economical viewpoint, it is preferably 0.05 to 0.5 equivalent.

The reaction pressure can be 15 to 160 kg / cm ² , but preferably 35 to 80 kg / cm ² .
At a lower pressure, the reaction intermediate remains, and at a higher pressure, the reactor is uneconomical. Reaction temperature is 25-160 ℃
However, it is preferably in the range of 50 to 120 ° C. If the temperature is lower than this range, the reaction rate will be significantly slower,
Further, at high temperatures, by-products increase, which is inconvenient.

The amount of ammonia used is 3-cyano-3,
1 to 40 for 5,5-trimethylcyclohexanone
It can be in the range of double molar equivalent, but it is preferably in the range of 2 to 8 molar equivalent. If too much ammonia is collected,
It is uneconomical in terms of reuse, and it is disadvantageous that too little ammonia increases by-products.

The organic solvent for the reaction includes, for example, alcohols such as methanol, ethanol and propanol; polyhydric alcohols such as ethylene glycol, propylene glycol and glycerin; cyclic ethers such as tetrahydrofuran and dioxane; methyltheosolve and ethyltheo. Preferable examples include theosolves such as solvable; methyltheosolve acetate, theosolve acetate such as ethyl ceosolve acetate, and polyethers such as diglyme and triglyme. In the present invention, the reaction can also be carried out without using a solvent. Thus obtained 3
From the reaction crude liquid of -aminomethyl-3,5,5-trimethylcyclohexylamine, a highly purified target product can be easily obtained by a known purification means, for example, distillation under reduced pressure.

[0028]

Industrial Applicability The method of the present invention uses silica or silica-alumina fine particle spherical catalyst carrying metallic cobalt as a catalyst, and the following method is used as compared with the conventional method using a catalyst prepared by crushing. Excellent in terms. Since the shape of the catalyst is almost constant and the change in particle size distribution and average particle size is small, the formation of the by-product 1,3,3-trimethyl-6-azabicyclo [3.2.1] octane is small and the selectivity is high. And the reaction yield is high. The surface of the catalyst is spherical and smooth, and there is little wear and pulverization of the catalyst during the reaction (change in particle size distribution and average particle size after the catalyst is used), and the catalyst removal operation when recovering and reusing the catalyst It's very easy. Since the catalyst has a good settling property, it can be easily separated from the reaction solution. Since catalyst wear and pulverization due to repeated use are small, there is little reduction in reaction activity and selectivity due to pulverization of the catalyst. Since the mole ratio of ammonia / CIP mole ratio is lowered, it is easy to recover ammonia. That is, the production method of the present invention is significantly superior to the conventional method in terms of productivity and catalyst cost such as improvement of reaction yield in continuous reaction, efficiency of catalyst recovery, and labor saving of catalyst separation operation.

[0029]

The present invention will be described in more detail below with reference to Reference Examples, Examples, Comparative Examples and Comparative Test Examples. The following examples are illustrative of the present invention and are within the scope of these examples. It is not limited. Further, although the spray drying method for silica is described in the reference example, the same method can be used for silica-alumina.

Reference Example 1: Preparation of catalyst by spray drying method (disk type method) Disk type spray dryer (diameter 2500 mm, height 5
(500 mm) and dried under the following conditions to obtain spherical products having an average particle size of 110 μm. Slurry component: 50% cobalt ion-supporting silica sol (prepared by coprecipitation method); Slurry concentration: 23.9% by weight; Specific gravity: 1.24; Viscosity: 0.65 poise;

Operating conditions Disk shape: 125 mm pin type; Rotation speed: 8000 rpm; Hot air inlet: 300 ° C .; Hot air outlet: 150 ° C .; Stock solution treatment rate: 19 kg / hr.

Reference Example 2: Spray drying method (nozzle type method)
Preparation of catalyst by nozzle type spray dryer (diameter 1800mm, height 1900m
m) and dried under the following conditions to obtain an average particle size of 154
A spherical product of μm was obtained. Slurry components: 50% cobalt ions carrying silica sol (adjusted with coprecipitation method); Concentration: 22.8 wt%; operating conditions nozzle type: two-fluid nozzle type; air pressure: 0.33 kg / cm ^2; hydraulic: 0.1 Kg / cm ² Nozzle: inner diameter 1.5 mm, outer diameter 10 mm; hot air inlet temperature: 300 ° C .; hot air outlet temperature: 120 ° C .; stock solution treatment rate: 2 kg / hr.

Example 1 A magnetic stirring type autoclave (capacity 0.3 liter) 50
% 1.5% of metallic cobalt-supported silica fine spherical catalyst was added,
3-Cyano-3,5,5-trimethylcyclohexanone (CIP) 15.6 g, methanol 115.2.g and ammonia 24.6 g were charged, hydrogen pressure 70 kg / cm ² , temperature 100 ° C.
And the reaction was carried out for 2 hours (rotor speed 850-950).
rpm). At this time, the pressure inside the autoclave is 70 kg / cm
Kept at ² . After cooling the autoclave, the pressure was released to make the residual pressure 5 kg / cm ² and the catalyst was filtered. As a result of quantitative analysis of the reaction crude liquid by gas chromatography, 3-aminomethyl-3,5,5-trimethylcyclohexylamine (I
PDA) was 85.9%. The other main by-products are 1,
3,3-Trimethyl-6-azabicyclo [3.2.1]
It was 7.1% in octane (TMAB). The reaction crude liquid was filtered off with a catalyst and the solvent was distilled off, followed by distillation under reduced pressure. The main distillate is as follows. IPDA: bp = 121 ° C. (11 mmHg); TMAC: bp = 64 ° C. (11 mmHg).

Example 2 A magnetic stirring type autoclave (capacity 0.3 liter) 33
% Metal cobalt-supported silica fine spherical catalyst 9.0 g,
CIP 60 g, methanol 93 g and ammonia 22.5
was charged, and the reaction was carried out for 2 hours at a hydrogen pressure of 70 kg / cm ² and a temperature of 110 ° C. (agitator rotation speed 850 to 950 rp).
m). At this time, the pressure inside the autoclave was maintained at 70 kg / cm ² . After cooling the autoclave, the pressure was released. As a result of quantitative analysis of the reaction crude liquid by gas chromatography, I
The PDA was 84.3%. Other major by-products are TMAB
Was 7.0%.

Example 3 A magnetic stirring type autoclave (capacity 0.3 liter) 20
% Metallic Cobalt-Supported Silica-Alumina Fine Spherical Catalyst 13.5
g, CIP 59.4 g, methanol 91.8 g and ammonia 22.8 g were charged, hydrogen pressure 70 kg / cm ² , temperature 10
The reaction was carried out at 0 ° C for 2 hours (agitator rotation speed 850-9
50 rpm). At this time, the pressure inside the autoclave is 70 kg
/ Cm ² was kept. After cooling the autoclave, the pressure was released. As a result of quantitative analysis of the reaction crude liquid by gas chromatography, IPDA was 82.4%. The other major by-product was TMAB at 6.5%.

Comparative Example 1 A reaction was carried out in the same manner as in Example 1 using 1.5 g of crushed silica catalyst carrying 50% metallic cobalt. As a result of quantitative analysis of the reaction crude liquid by gas chromatography, IPDA
It was 69.0%. The other major by-product is TMAB, 8.6%
Met.

Comparative Example 2 The same reaction as in Example 2 was carried out using 9.0 g of the crushed 33% metallic cobalt-supported silica catalyst. As a result of quantitative analysis of the reaction crude liquid by gas chromatography, IPDA
It was 65.2%. The other major product was TMAB at 8.3%.

Comparative Test Example 1: Measurement of catalyst sedimentation rate Crushed metallic cobalt-supported silica catalyst (particle size distribution 2 to 2)
00 μm) and metallic cobalt-supported silica fine spherical catalyst (particle size distribution 2 to 200 μm) were used in the reaction liquid of Example 1 (specific gravity 0.7).
8 、 viscosity 0.74 ~ 0.77cp 20 ℃)
The catalyst was suspended in the reaction solution having a height of m, and the time until most of the catalyst sinked was measured. The speed of the crushed metal cobalt-supported silica catalyst is 9.2 × 10 ^-4 cm / sec, while the speed of the metal cobalt-supported silica fine spherical catalyst is
It was 3.7 × 10 ^-2 cm / sec.

Comparative Example Test 2: Particle size distribution before and after use of the catalyst Metal cobalt-supported silica fine spherical catalyst (particle size distribution 2 to 2)
(00 μm) and a crushed metal cobalt-supported silica catalyst (particle size distribution of 2 to 200 μm) were repeated 20 times. The particle size distribution before and after use was measured by a laser diffraction light intensity measurement method. The obtained particle size distribution curves are shown in FIGS. The particle size of the metal-cobalt-supported silica catalyst crushed from the figure shifts to the smaller side after use (Figs. 3 and 4), but the metal-cobalt-supported silica fine spherical catalyst before and after use It can be seen that the change in particle size is small (FIGS. 1 and 2).

Comparative Example Test 3: Filterability of reaction solution 20 times repeated experiments were carried out under the conditions of Example 1, and the time required for filtering the reaction solution each time was measured. A 2 μm sintered filter was used as a filter. Dead volume of autoclave (40 ml) from the second reaction
The amount obtained by subtracting was added and the amount filtered was kept substantially constant. The filtration time was the time from the time when the reaction solution started to flow out to the time when the reaction solution started to flow after the reaction, after cooling the autoclave to room temperature, depressurizing and applying a new nitrogen pressure of 5 kg / cm ² . The results are shown in Table 1.

[0041]

[Table 1]

[Brief description of drawings]

FIG. 1 shows the particle size distribution of a metallic cobalt-supported silica fine spherical catalyst before repeated reaction.

FIG. 2 shows a particle size distribution of a metallic cobalt-supporting silica fine spherical catalyst after repeated reaction.

FIG. 3 shows the particle size distribution of the crushed silica catalyst carrying metallic cobalt before the repeated reaction.

FIG. 4 shows a particle size distribution of a crushed silica catalyst carrying metal cobalt after repeated reaction.

Continuation of front page (51) Int.Cl. ⁶ Identification number Office reference number FI technical display location // C07B 61/00 300

Claims (1)

[Claims] 1. 3-Aminomethyl-reaction of 3-cyano-3,5,5-trimethylcyclohexanone with ammonia and hydrogen in the presence or absence of an organic solvent.
3-Aminomethyl-3,5,5-trimethylcyclohexylamine, characterized in that in the method for producing 3,5,5-trimethylcyclohexylamine, silica loaded with metallic cobalt or silica-alumina fine spherical catalyst is used. Manufacturing method.