JPH0820562A - Production of tertiary butyl amine - Google Patents

Abstract

PURPOSE:To obtain a tertiary butyl amine useful as synthetic raw material for rubber chemical, agrichemical, pharmaceutical, etc., by reacting isobutene or tertiary butyl alcohol with ammonia in the presence of a metal in a single process. CONSTITUTION:This tertiary butyl amine is obtained by reacting isobutene or tertiary butyl alcohol with ammonia in the presence of at least one kind of element selected from Ru, Os, Pd and Pt at 150-400 deg.C under a gage pressure of 0-300kg/cm<2>. The metal is used in the form of a catalyst, preferably carried on a carrier (e.g. zeolite or active carbon). The carrying ratio of the metal is 0.1-50wt.%. The metal can keep high catalytic activity for a long time and enables the production of tertiary butyl amine in a high rate reaction and in high space time yield.

Description

Detailed Description of the Invention

[0001]

BACKGROUND OF THE INVENTION 1. Field of the Invention The present invention relates to a method for producing tertiary butylamine (hereinafter abbreviated as t-butylamine), and more specifically, isobutene or tertiary butyl alcohol (hereinafter abbreviated as t-butyl alcohol) and ammonia. To a method for producing t-butylamine by a one-step reaction operation using a catalyst. T-butylamine is a useful compound used as a synthetic raw material for rubber chemicals, agricultural chemicals, pharmaceuticals and the like.

[0002]

2. Description of the Related Art It is well known that t-butylamine can be produced by reacting isobutene or t-butyl alcohol with ammonia in the presence of a catalyst.
For example, J. Org. Chem., 53 , 4594-4596 (1988), it is described that t-butylamine can be obtained by reacting isobutene and ammonia with silica-alumina or zeolite as a catalyst. Also, in JP-A-1-75453, an amine in which a reaction mixture of an olefin having 2 to 8 carbon atoms and a nitrogen compound such as ammonia is reacted in the presence of a dealuminated crystalline aluminosilicate. Is disclosed.

If t-butylamine is produced by the above-mentioned method, a method which has been widely used industrially to date,
That is, a reaction of isobutene and hydrocyanic acid to form an acid amide, a method of treating it under alkaline conditions to eliminate sodium formate (US Pat. No. 4,131,642), reacting t-butyl alcohol and hydrocyanic acid, and then A method of reacting this with methanol and water in the presence of an acid catalyst to obtain the desired product and methyl formate (European Patent No. 50,870), methyl-t
-A method of reacting butyl ether with hydrocyanic acid and then refluxing it in a mixed solvent of water and methanol (European Patent No. 5
0,869) and the like to produce t-butylamine,
There are various advantages such as the reaction process is simple and simple, a toxic and difficult-to-handle substance such as hydrocyanic acid is not used, and by-products such as formic acid are not generated.

[0004]

However, the above-mentioned method using silica-alumina or zeolites as a catalyst cannot be said to be sufficiently satisfactory for industrially producing t-butylamine. That is, in these methods, the activity of the catalyst is decreased during the reaction, and it is difficult to produce t-butylamine in a long-term continuous operation.
Furthermore, with these catalysts, the reaction rate of isobutene or t-butyl alcohol with ammonia is relatively small, and the space-time yield of the resulting t-butylamine is low, and the performance as a catalyst can withstand industrial operations. There is a problem that you have not reached the level.

Therefore, in the present invention, a method for producing t-butylamine by reacting isobutene or t-butyl alcohol with ammonia to enable continuous operation for a long time and further to obtain a sufficient reaction rate and product yield is provided. The purpose is to provide.

[0006]

The present inventors have reacted with isobutene or t-butyl alcohol with ammonia,
In producing t-butylamine, extensive research and studies were conducted on catalysts that can be used for it. As a result, when the reaction is carried out in the presence of ruthenium, osmium, palladium, platinum, or a compound of these metals, t-butylamine is obtained particularly rapidly and in good yield, and further, the activity of the catalyst is significantly decreased. The present invention has been completed by finding that it is extremely small and can be adopted as a sufficiently industrial manufacturing method.

That is, according to the present invention, when isobutene or t-butyl alcohol is reacted with ammonia to produce t-butylamine, the reaction is carried out in the presence of one or more elements selected from ruthenium, osmium, palladium or platinum. And a method for producing t-butylamine.

In the method of the present invention, the above metal element is
The catalyst may be used by dispersing it in the reaction medium in the form of a simple substance or a compound, but from the viewpoint of increasing the surface area and stabilization, the catalyst may be used by supporting it on a suitable carrier. More preferable.

When supported on a carrier, suitable carriers are those widely used as general catalyst carriers, for example, diatomaceous earth, zeolite, silica-alumina,
Alternatively, activated carbon or the like can be used. The loading ratio of the catalyst metal on the carrier is usually 0.1 to 50% by weight, more preferably 1 to 10% by weight.

Further, various methods for supporting the carrier can be selected. In this case, the form of the catalyst raw material metal is a ruthenium, osmium, palladium, or platinum halide, acetate, sulfate, nitrate, or a metal complex thereof, for example, an amine complex, a carbonyl complex, a phosphine complex, or a cyano complex. Etc. can be used.

When the catalyst is prepared by using these metal raw material species and supporting them on a carrier, a general preparation method such as a conventionally known impregnation method or ion exchange method can be widely adopted. For example, in the impregnation method, one or more of the above-mentioned metal compounds or metal complexes are dissolved in water, and then a carrier is added to the solution to sufficiently impregnate it with 100-
It can be prepared by drying at about 140 ° C. and then baking at 300 to 700 ° C. Usually, after the calcination, the above-mentioned metal compound becomes a metal oxide and is supported on a carrier. Further, a catalyst in which a single metal is supported is prepared by reducing the metal compound in hydrogen. Can be used, and any of them is useful for the production method of the present invention. It can also be prepared by an ion exchange method by using zeolite and performing ion exchange with metal ions contained therein.

In the method of the present invention, the form of the catalyst to be used is not particularly limited and may be appropriately selected from a wide range such as powder, extruded product, compression molded tablet, and crushed product having an appropriate size. It can be selected and used.

Isobutene or t-
In the process of the present invention in which the reaction of butyl alcohol and ammonia is carried out, the reaction temperature is in the range of 150 to 400 ° C, more preferably 200 to 300 ° C. Also, the pressure is normal pressure ~
Can be performed in a wide range under high pressure, usually 0 ~
The range of 300 kg / cm ² · G is often used. The value of the molar ratio (C ₄ / NH ₃ ) of ammonia and isobutene or t-butyl alcohol used in the reaction is in the range of 1/1 to 1/10, and the range of 1/1 to 1/5 is usually used. It

In the method of the present invention, a liquid phase reaction in which isobutene or t-butyl alcohol is reacted with ammonia while suspending the catalyst in the liquid phase is also possible, but it is usually a fixed bed reactor or a fixed bed. It is carried out by a gas phase reaction using the multi-tube reactor. When carrying out in a gas phase reaction, the feed rate of the reaction mixture of isobutene or t-butyl alcohol and ammonia to the catalyst layer is usually GHSV (gas space velocity,
Calculated as NTP, 200 to 10,000 hr ^-1 , more preferably 500
It is in the range of ~ 3000 hr ^-1 .

[0015]

EXAMPLES Hereinafter, the method for producing t-butylamine of the present invention will be described in more detail with reference to examples. In the following, the conversion rate of the raw materials and the selectivity of the target substance are the results calculated from the values obtained by analyzing the reaction products by gas chromatography.

Example 1 In 50 g of water, ruthenium (III) chloride.nH ₂ O (n = 1 to 1)
3) 1 g was dissolved, 10 g of diatomaceous earth was added thereto, and the mixture was stirred and dried at 130 ° C. for 2 hours to evaporate water. Next, this was calcined at 500 ° C. for 4 hours to prepare a catalyst. When analyzed by fluorescent X-ray analysis (XRF) measurement, it was confirmed that ruthenium oxide was carried in the prepared catalyst at a ratio of 8% by weight. Next, using a Pyrex glass tube (internal diameter 12 mm), 5 ml of the catalyst obtained above was filled, and further, an alumina ball having a diameter of 3 mm was filled in the upper part of the catalyst to prepare a reactor for vaporizing a raw material. It was made. This reactor was fixed in an electric tubular furnace maintained at a temperature of 250 ° C, and a mixture of t-butyl alcohol and ammonia (molar ratio of C ₄ / NH _{3 was} added while flowing nitrogen gas at 10 ml / min from the upper part of the reactor. = 1/3) GHSV = 2000hr ^-1
Was continuously supplied, and the reaction was carried out under normal pressure. When the reaction product was collected in a cooling trap and quantitatively analyzed, the conversion of t-butyl alcohol was 15% and the selectivity of t-butylamine was 15%.
The target compound was continuously obtained at 97 mol%. In this continuous reaction operation, the activity of the catalyst did not decrease even after 3 hours, and the same active state as the initial state was maintained.

Example 2 The same procedure as in Example 1 was repeated except that zeolite was used in place of the diatomaceous earth used in the catalyst preparation, and isobutene was used in place of t-butyl alcohol as a raw material. Was done. The results are shown in Table 1. In addition, it was confirmed that the activity of this catalyst did not decrease and that the same active state as in the initial state was maintained even after 3 hours.

Example 3 In the same manner as in Example 1, except that zeolite was used as a carrier for preparing a catalyst and palladium chloride was impregnated into the carrier to carry out the same preparation, and a catalyst supporting palladium oxide was used. All were operated under the same conditions to carry out the reaction. The results are shown in Table 1. Also in this case, the activity of the catalyst used did not decrease, and it was confirmed that the same active state as in the initial state was maintained even after 3 hours.

Examples 4 to 6 Zeolite was used as a carrier for catalyst preparation, and palladium chloride, platinum chloride, or osmium chloride was separately impregnated into the carrier, and the same preparation operation as in Example 1 was performed to prepare each metal species. A supported catalyst of was prepared. Using these catalysts, Table 1
Using the raw materials shown in Table 1, under the same reaction conditions as in Example 1, t-
Butylamine was produced. The results are shown in Table 1. The activity of the catalysts used for these catalysts was not decreased in any of the catalysts, and they remained in the same active state as the initial state even after 3 hours.

Comparative Example 1 A method described in JP-A-1-75453, that is, a mordenite catalyst (Si / Al molar ratio = 6.1) prepared by treating a crystalline aluminosilicate with hydrochloric acid and dealumination is used. Then, t-butylamine was produced by operating under the same conditions as in Example 1 except that 5 ml of this was charged into the reactor. In this case, the conversion of t-butyl alcohol was 8.5%, and the selectivity of t-butylamine was 95%. In this continuous reaction operation, signs of catalyst deterioration were observed with the passage of time, and it was confirmed that the activity was obviously lower than that of the initial stage after 3 hours.

[0021]

[Table 1]

[0022]

As described above in detail, according to the method for producing t-butylamine of the present invention, the performance of the catalyst used in the reaction can be kept high for a long period of time, and the reaction rate of ammonia with isobutene or t-butyl alcohol. And the space-time yield of t-butylamine is greatly improved. Therefore, it is a suitable method for industrially producing t-butylamine, and the significance of enabling this is extremely great.

─────────────────────────────────────────────────── ─── Continuation of the front page (51) Int.Cl. ⁶ Identification code Internal reference number FI technical display location C07C 209/16 209/60 // C07B 61/00 300

Claims (1)

[Claims] 1. When producing tertiary butyl amine by reacting isobutene or tertiary butyl alcohol with ammonia, the reaction is carried out in the presence of at least one element selected from ruthenium, osmium, palladium or platinum. A method for producing tertiary butylamine.