A method of obtaining a palladium hydrogenation catalyst

 

The invention relates to the field of physical chemistry and can be used to regulate the speed of the auto-catalytic hydrogenation reactions. In the method of obtaining a palladium hydrogenation catalyst by restoring divalent palladium starting compound and deposition of the recovered palladium on carbon material as a starting compound used tetraamminepalladium (II) perchlorate, and the recovered palladium precipitated on the carbon nanomaterial; as the carbon nanomaterial can use the fullerene C60carbon nanotubes, cathodic Deposit; as the carbon nanomaterial can use a mixture of fullerenes With60and C70in the following ratio, wt.%: fullerene C60- 60-80, fullerene C70- 20-40. Thus the task of creating a method of obtaining a palladium hydrogenation catalyst, which has a higher catalytic activity and operates in more mild conditions (at room temperature and normal (atmospheric) pressure. 4 C.p. f-crystals, 5 Il.

The invention relates to the field of physical chemistry and is tiravanija relate to major industrial processes, implemented, as a rule, in the presence of a catalyst, in particular, for the synthesis of acyclic and cyclic saturated organic compounds, high-quality gasoline and so on

According to literature data (Grove D. E. Plat. Met., 2002, 46, (2) 92) about 75% of the industrial hydrogenation processes is carried out on Pd/C catalyst containing 5% palladium metal. Rich catalytic chemistry of palladium covers virtually the entire spectrum of reactions required for organic synthesis. Thus, Pd/C is currently the most successful system for the implementation of catalytic organic synthesis.

A known method of obtaining a palladium hydrogenation catalyst by restoring divalent palladium starting compound and deposition of the recovered palladium on carbon material, where the parent compounds are complexes of Pd (II) Tsuji, J. Palladium reagents and catalysts-innovations in organic syntheses. John Wiley & sons, Chichester, 1995, 595 p.; Grove, D. E. Plat. Met., 2002, 46, (1) 48.

There is also known a method of obtaining a palladium hydrogenation catalyst by restoring divalent palladium starting compound and deposition of the recovered palladium on carbon material, with the new path organic synthesis”), translation from English, M. S. Ermolenko and C. G. Kiseleva, M.: Chemistry, 1989, S. 361.

A solution of palladium chloride (8.2 g) in chloroethanol acid (20 ml of concentrated acid in 50 ml of water) is heated with stirring for 2 h, added with stirring to a hot (80° C) suspension of coal in water (93 g in 1.2 l of water), pre-washed with nitric acid.

You can use almost any coal with a sufficiently large specific surface treated with nitric acid (10%) for 2-3 h, followed by rinsing with water to remove the acid and dried at 100° C. Then added formaldehyde (8 ml of 37% solution) and sodium hydroxide solution until alkaline reaction. After 10 min the catalyst is filtered off, washed with water (10× 250 ml) and dried in vacuo over calcium chloride. The output of palladium 5% on coal 93-98%.

This method is adopted as the prototype of the present invention.

Its disadvantage is a small amount of activity obtained according to the method of the catalyst, the need for the implementation of the process of catalysis elevated (more than 60° C) temperature and pressure (above 5 MPa). This is due to the complexity of the activation reaction sites of the catalyst obtained by the JV is laisteridge hydrogenation catalyst, who would have greater catalytic activity and worked in more mild conditions (at room temperature and normal (atmospheric) pressure).

According to the invention this problem is solved due to the fact that the method of obtaining a palladium hydrogenation catalyst by restoring divalent palladium starting compound and deposition of the recovered palladium on carbon material as a starting compound used tetracaprylate perchlorate, and the recovered palladium precipitated on the carbon nanomaterial; as the carbon nanomaterial can use the fullerene C60in the carbon nanomaterial can use carbon nanotubes in the carbon nanomaterial can use cathode Deposit; as the carbon nanomaterial can use a mixture of fullerenes With60and C70in the following ratio, wt.%:

Fullerene C6060-80

Fullerene C7020-40

The applicant has not identified the sources containing information about technical solutions, identical to the present invention, which allows to make a conclusion about its compliance with the criterion of “novelty”.

Implementation distinctive panago connection tetracaprylate (II) perchlorate is large dispersion of the recovered material (palladium); the deposition of the carbon nanomaterial dictates the retention of palladium nanocluster form.

These circumstances greatly increase the catalytic activity of the product resulting from the implementation of the method, determine the possibility of catalysis at room temperature and normal atmospheric pressure.

The applicant has not found any sources of information containing data about the impact of an alleged distinguishing signs on achieved as a result of their implementation of the technical result. This, according to the applicant demonstrates compliance with this technical solution, the criterion of “inventive step”.

In Fig.1 is a diagram of an installation for implementing the inventive method of obtaining a palladium hydrogenation catalyst.

In Fig.2 is a graph illustrating the dependence of the volume absorption of the gas mixture in the presence of a catalyst obtained according to the method according to p. 2 claims in various hydrogenation reactions:

(1) C2H4+H4With2H6;

(2) CH2=SNSN2HE+H2SNsub>aq+2H+.

in Fig.3 - same as in Fig.2, in the presence of a catalyst obtained according to p. 3 claims;

in Fig.4 is the same as in Fig.2, in the presence of a catalyst obtained according to p. 4 claims;

in Fig.5 is the same as in Fig.2, in the presence of a catalyst obtained according to p. 5 claims.

Installation for implementing the method comprises a reactor 1 with a mixing device 2. Hydrogen is in the tank 3. The reactor 1 is connected to a gauge installation 4.

In the first specific example, the method is implemented as follows.

In the reactor 1 is placed 2.0 l of distilled water, bring to 600 mg of carbon nanomaterials, in particular fullerene C60add 5,22 ml 5,7· 10-2m solution of [Pd(H2O)4(ClO4)2containing 0.7 m perchloric acid, and stirred for 0.5 hour. Then perform the recovery of divalent palladium by passing through the prepared solution of hydrogen for 2 hours.

The precipitate is filtered on the filter SCHOTT, washed repeatedly with distilled water and dried in a vacuum desiccator over P2O5within two days. The output of the catalyst was 98-99% (catalyst I).< used carbon nanotubes; in the third example (catalyst III) used cathode Deposit; in the fourth example (catalyst IV) as a carbon nanomaterial used a mixture of fullerenes With60and C70in the following ratio, wt.%:

Fullerene C6060-80

Fullerene C7020-40.

Each catalyst was tested in the three above hydrogenation reactions. For this purpose, the catalyst in an amount of 10 mg was placed in the reactor and added in the case of reaction (1) 10 ml of distilled water, reaction (2) to 10 ml of an aqueous solution of 0.01 ferric sulphate reactions (3) to 10 ml of 0.002 m aqueous solution of allyl alcohol. In the case of reaction (1) the reactor was filled eilenodontini mixture with a volume ratio of 1:1, in the case of reactions (2), (3) is hydrogen. The reaction was carried out at a temperature of 18-25° C and normal atmospheric pressure. Reaction speed(1), (2), (3) register for changing the volume of absorbed gases in time in the presence of catalysts I, II, III, IV (Fig.2, 3, 4, 5, respectively).

For comparison, in similar conditions was determined by the rate of hydrogenation in the presence of an industrial catalyst is Pd/C. In the reaction (1) this rate does not exceed 10-12% of the speed of hydrogenation in the presence of catalysts I, II, III, IV, reaction (2) hydrogenation PP-top:2mm;">Claims

1. A method of obtaining a palladium hydrogenation catalyst by restoring divalent palladium starting compound and deposition of the recovered palladium on carbon material, characterized in that as starting compounds are used tetraamminepalladium (II) perchlorate, and the recovered palladium precipitated on the carbon nanomaterial.

2. The method according to p. 1, characterized in that the carbon nanomaterial use fullerene C60.

3. The method according to p. 1, characterized in that the carbon nanomaterial use carbon nanotubes.

4. The method according to p. 1, characterized in that the carbon nanomaterial use of the cathode Deposit.

5. The method according to p. 1, characterized in that the carbon nanomaterial use a mixture of fullerenes With60and C70in the following ratio, wt.%:

Fullerene C6060-80

Fullerene C7020-40



 

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