The catalyst for the reductive alkylation of 4 - aminodiphenylamine acetone and hydrogen to n-isopropyl-n'- phenyl-p-phenylenediamine and its production method

 

(57) Abstract:

The invention relates to catalysts for the reductive alkylation of 4-aminodiphenylamine acetone and hydrogen to N-isopropyl-N-phenyl-p-phenylenediamine (diafana OP, IPPD) and methods for their preparation. The catalyst contains copper oxide and aluminium oxide in the following ratio, wt. %: CuO 33-41, Al2O359-67. The method of producing the catalyst is in the mixing of aqueous solutions of copper nitrate, aluminum nitrate and ammonium carbonate, followed by filtration of the suspension, washing and granulating the obtained paste, drying, and grinding of pellets and calcining the resulting powder at 355-460oC for 4 h, the Catalyst does not contain environmentally hazardous components and has a high activity and selectivity. 2 S. p. f-crystals, 1 table.

The invention relates to catalysts for the reductive alkylation of aromatic amines with aldehydes or ketones and hydrogen, and more particularly to catalysts for the reductive alkylation of 4-aminodiphenylamine (ADPA) acetone and hydrogen to N-isopropyl-N'-phenyl-p-phenylenediamine (diafana AF) and methods for their preparation.

There are several katalizatorye iron or manganese (Patent Germany 1077667, CL 12 G 5, 1960 Patent UK 804113, CL 25 R, 1968) and their oxides (Japan Patent 15601, CL 2-2225, 1968 USSR Author's certificate 961295, CL 07 C 87/58//01 J 23/70. Declared 22.10.80).

The main disadvantage of these catalysts is the presence in the catalyst of environmentally hazardous compounds chromium.

Also known catalyst for the reductive alkylation of ADFA acetone and hydrogen to deafen OP containing copper and aluminum or chromium (III) in an atomic ratio (0.6 to 0.9):1, and the method of its production by co-precipitation at pH (6.0 and 7.0) and temperature (40-85)oC followed by heat treatment, characterized in that the coprecipitation are from a mixture of aqueous solutions of the nitrates of copper and aluminum or chromium (III) solution of carbonate or bicarbonate of an alkali metal, or ammonium, and the heat treatment of the obtained gidroksicarbonata copper - aluminum or chromium (III) with the structure of hydrotalcite carried out at 250-350oTo obtain a catalyst with an atomic ratio of copper-chromium (III) or aluminum (0,6-0,9): 1 (Patent of the Russian Federation 2053842, 10.02.96. Bull. 4) prototype.

The disadvantage of the catalyst of the prototype is the complexity of its structure type hydrotalcite, the achievement of which in industrial conditions ol the b preparation of the catalyst of the prototype has several disadvantages.

For sasodei use aqueous solutions of copper nitrate, aluminum nitrate and ammonium carbonate with the mass fractions of these components equal to 10% (100 g/l). So after filtration of the resulting suspension is formed overestimated the amount of leachate that makes its reuse, recycling or disposal and leads to excessive loss of the original components.

- Drying the resulting paste is uneven and delayed in time.

- The calcination of the dried paste is uneven and swelling, making it further grinding, and the temperature within the annealing (250-350)oTo not allow to obtain the catalyst in the form of a mixture of oxides of copper and aluminum.

The objective of the invention is to create a catalyst based on oxides of copper and aluminum that do not contain chromium compounds, while maintaining high activity and selectivity in the reaction of reductive alkylation of ADFA acetone and hydrogen to deafen OP, and also create a way for this catalyst, which is devoid of the disadvantages of the method on the prototype. This is achieved by the catalyst according to the invention, comprising a copper oxide (CuO) and aluminum oxide (Al2oAnd pH of the medium (6,0-7,0) units pH, filtering the resulting suspension, washing and granulating the obtained pastes, granules drying, grinding the pellets into a powder and annealing the powder for 4 h at (355-460)oC.

The difference of the catalyst according to the invention of the catalyst of the prototype is that the catalyst comprises oxides of copper and aluminum in the following ratio, wt.%:

SiO - 33-41

Al2O3- 59-67

The difference of the method of preparation of the catalyst according to the invention from the way the prototype is that the mass fraction of copper nitrate, aluminum nitrate and ammonium carbonate in the original solution is 20%, the washed paste before drying granularit and the dried granules before annealing is ground into powder, which is calcined at a temperature of (355-460)oWith obtaining a catalyst according to the invention.

The possibility of carrying out the invention is illustrated by the following examples.

Example 1.

In a glass flask with a capacity of 2.0 DM3mix 1054 cm3water rastakraut 60o(Solution 1). Separately prepare 3,0 DM3an aqueous solution containing 20 wt.% carbonate of ammonia (solution 2). In a glass reactor with a capacity of 5.0 DM3with a stirrer, thermometer, heating system and the electrodes measure the pH of the medium load 500 cm3distilled water, include a stirrer, heating and operating the stirrer in the reactor serves both solution 1 and solution 2, and the feed rate of solution 2 is adjusted so that during mixing, the pH was equal to (6,0-7,0) units of pH. When mixing solutions of the temperature in the reactor is maintained within the range (40-60)oC. After filling the reactor feed solutions and cease doing endurance 1 h under stirring and the temperature (65-70)oC. the Precipitate from the resulting suspension are filtered. The paste is washed with water and granularit. The granules are dried at a temperature (100-120)oWith up to a residual water content of not more than 5.0 wt.%. The dried granules are crushed into powder, which is calcined at a temperature of (355-460)oC for 4 h Get 100 g of catalyst a mixture of oxides of copper and aluminum in the following ratio, wt.%:

SiO - 41

Al2O3- 59

Example 2.

What SUP> an aqueous solution containing 20 wt.% nitrate of copper. Further preparation of the catalyst is carried out as described in example 1. Get 100 g of catalyst a mixture of oxides of copper and aluminum in the following ratio, wt.%:

SiO - 37

Al2O3- 63

Example 3.

Prepare a solution of 1 mixing 1197 cm3an aqueous solution containing 20 wt. % of aluminium nitrate, 328 cm3an aqueous solution containing 20 wt.% nitrate of copper. Further preparation of the catalyst is carried out as described in example 1. Get 100 g of catalyst a mixture of oxides of copper and aluminum in the following ratio, wt.%:

SiO - 33

Al2O3- 67

Example 4.

This example shows the catalytic activity of the catalyst according to the invention in the reaction of reductive alkylation of ADFA acetone and hydrogen to deafen AF.

In the autoclave with a capacity of 0.5 DM3with a stirrer, a heating system, a thermocouple and pressure gauge load 92 g ADFA, 120 cm3acetone and 1.8 g of the catalyst obtained in example 1. The autoclave is pressurized, rinsed with hydrogen, raising the hydrogen pressure in the autoclave up to 3.5 MPa, include a stirrer and heated the contents of the autoclave to 150oC. P is shown in the table.

Example 5.

Under the conditions of example 4, the tests of the catalyst obtained according to example 2. The test result shown in the table.

Example 6.

Under the conditions of example 4, the tests of the catalyst obtained according to example 3. The test result shown in the table.

The results of the tests of the catalyst according to the invention confirm its high activity and selectivity, which proves its suitability for industrial use in the production of diafine OP.

1. The catalyst for the reductive alkylation of 4-aminodiphenylamine acetone and hydrogen to N-isopropyl-N-phenyl-p-phenylenediamine, including copper oxide (CuO) and aluminum oxide (Al2ABOUT3) in the following ratio, wt.%:

Cu - 33-41

Al2O3- 59-67

2. The method of producing catalyst according to p. 1 by mixing aqueous solutions of copper nitrate, aluminum nitrate and ammonium carbonate at a temperature of 40-85oC and a pH of 6.0-7.0 pH units, filtration, washing and drying the resulting paste with subsequent annealing, characterized in that the mass fraction of copper nitrate, aluminum nitrate and ammonium carbonate in the original solutions equal to 20%, before drying the indicate when the temperature 355-460oC obtaining catalyst under item 1.

 

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