Palladium hydrogenation catalyst and method to manufacture thereof

FIELD: CHEMISTRY.

SUBSTANCE: palladium hydrogenation catalyst is described. It contains reduced palladium compound and modifier, where palladium bis-acetylacetonate is used as starting palladium compound and white phosphorus (Р4) is used as modifier, component ratio being as follows: palladium bis-acetylacetonate/phosphorus =1:0.1 to 1:1. Method to manufacture thereof is also described. The said method is based on reduction of the starting palladium compound with hydrogen in the presence of modifier. White phosphorus is used as modifier and is introduced prior to reduction of palladium (II) compound with hydrogen, palladium bis-acetylacetonate being used as starting compound, at optimum for catalyst system formation temperature of 80-90°С (353-363 К) and optimum for catalyst formation time of 25-30 minutes.

EFFECT: increase in catalyst activity, when catalytic process takes place under mild conditions.

2 cl, 5 tbl, 25 ex

 

The present invention relates to the field of catalytic chemistry, in particular the development of effective catalyst for the hydrogenation of unsaturated hydrocarbons (alkenes, alkynes), carbonyl and nitro compounds and method of its production, and can be used in fine organic synthesis.

A known method of obtaining a palladium catalyst in the hydrogenation of unsaturated compounds by reduction with hydrogen tetraamminepalladium (II) perchlorate and deposition restored nonvalence palladium on carbon material - nanocluster soot separate portions [RF Patent №2258561, B01J 23/44, B01J 21/18, B01J 37/18, B01J 37/03, 2005].

The disadvantage of the catalyst-analogue is a low catalytic activity in the hydrogenation of alkenes, which does not exceed 580 mol of ethylene/mol Pd·h (10 mol of ethylene/mol Pd·min) at a temperature of 25°and a hydrogen pressure of 1 ATM.

A method of obtaining a heterogeneous palladium catalyst hydrogenation by fixing tetrachloropalladate potassium (K2PdCl4) laminirovannom chlorotoluene copolymer of styrene and divinylbenzene with a particle size of the carrier of 0.075-0.12 mm, and subsequent reduction of the obtained metallopolymer with sodium borohydride [2039599 C1, B01J 37/00, B01J 23/44, 1995]. The disadvantage of the catalyst-analogue is low kata is itihasa activity in the hydrogenation of nitrobenzene, which does not exceed 30 mol of nitrobenzene/mol Pd·min (the reaction rate 14,42 ml of N2/min when loading a heterogeneous catalyst containing 1 wt.% Pd, 0.2 g; temperature, 45°and a hydrogen pressure of 1 ATM).

A method of obtaining palladium catalyst hydrogenation of acetylene compounds by interaction π-allylchloroformate with hydrazine in a molar ratio of hydrazine and π-allylchloroformate 1.5 to 2.5:1 [Ed. mon. The USSR 1100775 a, class 01J 37/16, 23/44, 1985].

The disadvantage of the catalyst-analogue is a low catalytic activity in the hydrogenation of alkynes, in particular phenylacetylene, which does not exceed 9800 ml phenylacetylene/g Pd·min (43 mol of phenylacetylene/mol Pd·min) at a temperature of 20°and a hydrogen pressure of 1 ATM and selectivity to styrene 95-96% at the time of absorption half of the calculated amount of hydrogen. The ratio of phenylacetylene:catalyst = 500.

Known homogeneous catalyst for the hydrogenation based on binuclear palladium complex of the composition [(But2PH)Pd(μ-PBut2)]2that with a selectivity of 98% hydrasuit cyclooctadiene-1,3 at 20°and a hydrogen pressure of 1 ATM in an environment THF. This catalyst exhibits catalytic activity only after first interacting with a molecular key is activated oxygen [I.S. Cho, Alper H. Selective Hydrogenation of Simple and Functionalized Conjugated Dienes Using a Binuclear Palladium Complex Catalyst Precursor. // Tetrahedron Letters. - 1995. - V.36, N 32. P.5674].

The disadvantage of the catalyst is a complex multistage synthesis source binuclear complex of palladium - [(But2PH)Pd(μ-PBut2)]2.

Known hydrogenation catalyst on the basis of the acetate complex of palladium (II) with tridentate P-, N-, O-containing ligand of the structure of [Pd(OAc)(PPh2(C6H4)CH=N-N=C(O)(CH3)], which hydrasuit unsaturated hydrocarbons under mild conditions (at a temperature of 40°and a hydrogen pressure of 1 ATM) [A. Bacchi, Carcelli M., M. Costa, A. Leporati, Leporati E., P. Pelagatti, Pelizzi S., G. Pelizzi Palladium (II) complexes containing a P, N-chelating ligand. Part II. Synthesis and characterization of complexes with different hydrazinic ligands. Catalytic activity in the hydrogenation of double and triple C-C bonds. // J Were Obtained. Chem. - 1997 - V.535. - P.107-120]. The disadvantage of this catalyst is the low catalytic activity in the hydrogenation of styrene and not more than 0.1 mol/g-al-Pd-min, and in the hydrogenation of Talana is 0.4 mol/g-al-Pd-min, as well as the complexity of the synthesis tridentate P-, N-, O-ligand.

The closest known solution of an analogous problem to the technical essence and the achieved effect is a method for the catalytic hydrogenation of unsaturated compounds by restoring the bis-acetate palladium hydrogen in benzene in the presence of triphenylphosphine p and a temperature of 20° C and a hydrogen pressure of 1 atmosphere for 1 h and a hydrogenation catalyst containing bis-acetate, palladium and modifying additive - triphenylphosphine, in which the ratio of Pd:P=1:1 [siksak A., Ungvary F., Kiss G. The formation of Catalytically active species by the reduction of palladium carboxylate phosphite systems: 1. Hydrogenation's // J. Mol. Catal. - 1983. - Vol.18, No. 2. - P.229]. The maximum specific activity of the catalytic system [Pd(OAc)2]3+3h3in the hydrogenation of ethynylbenzene (phenylacetylene) at 20°and the hydrogen pressure 1 excessive atmosphere is 4.8 mol/g-at Pd·min, in the hydrogenation of styrene and 0.2 mol/g-at Pd·min. Ratio of substrate: palladium = 1000.

Its disadvantages are the need for preliminary multi-stage synthesis of triphenylphosphine and low specific catalytic activity in hydrogenation as terminal alkynes (phenylacetylene)and alkenes (styrene).

The task of the invention is the creation of a palladium hydrogenation catalyst, which would have a large catalytic activity, could carry out a catalytic process under mild conditions (at room temperature and normal (atmospheric) pressure), as well as reduce the cost of implementation of the method.

This object is achieved in that the hydrogenation catalyst containing the recovered compound of palladium and modifying doba is ku, as the source of palladium compounds using bis-acetylacetonate, palladium, and as a modifying additive white phosphorus (P4) in the following ratio of components: bis-acetylacetonate palladium/phosphorus = 1:0.1 to 1:1.

This object is achieved in that in the method of producing catalytic hydrogenation, based on recovery of starting compound of palladium with hydrogen in the presence of the modifying additive, as modifying additives used white phosphorus, which is injected to the stage of recovery of the compounds of palladium (II) hydrogen, and as the parent compound of palladium bis-acetylacetonate, palladium, at the optimal temperature for the formation of catalytic systems 80-90° (353-363 K) and the optimal time of formation of the catalyst 25-30 minutes

A distinctive feature of the present invention is used as a modifying additive white phosphorus introduced into the reaction system to the stage of recovery of Pd(acac)2hydrogen, as well as the simplicity of its receipt.

The proposed method is efficient palladium catalyst for the hydrogenation of unsaturated, carbonyl and nitro compounds is as follows:

To a solution of bis-acetylacetonate palladium in DMF, placed in a thermostatted vessel type "duck"when room is the temperature in a stream of hydrogen add a solution of white phosphorus in benzene. The reaction mixture is stirred in hydrogen atmosphere at a temperature of 80-90° (353-363 K) for 15-30 min before the formation of the "solution" of black and brown. Then the reaction mixture is cooled to 30°and used in the hydrogenation.

Optimal conditions for the formation of the catalyst: the ratio of bis-acetylacetonate palladium:phosphorus = 0.2 and 0.3 (table 1); the temperature recovery of palladium (II) hydrogen 80-90° (353-363 K) (table 2), the recovery time is 25-30 min (table 3); the concentration of Pd(acac)2- 1 mmol/l (table 4).

Thus obtained catalyst allows gidrirovanii at a temperature of 30°C (303 K) styrene with activity 280 mol H2·(d) ATA Pd·min)-1; phenylacetylene consistently gidrirovanii to styrene with activity 157 mol H2·(d) ATA Pd·min)-1(if conversion phenylacetylene 90,0% selectivity to styrene is 95,3%) and then to ethylbenzene activity 118 mol H2·(d) ATA Pd·min)-1; nitrobenzene activity 128 mol H2·(d) ATA Pd·min)-1and 100%selectivity for aniline, benzaldehyde with activity 15 mol H2·(d) ATA Pd·min)-1and 100% selectivity for benzyl alcohol at 90% conversion (table 5).

Its advantage in comparison with the prototype is the higher specific catalytic activity in the hydrogenation.

Prima is 1: To a solution of 0,00304 g (1· 10-5mol) Pd(Acac)2in 9 ml of DMF, placed in otakuminopera, the hydrogen-filled vessel type "duck"add to 0.3·10-5mol of white phosphorus (P4) in 1 ml of benzene and stirred the reaction mixture for 25 min at 80°and the hydrogen pressure 1 excessive atmosphere. Received black-and-brown "solution" is cooled to 30°C (303 K) and experience in the hydrogenation of styrene. For this purpose through a Teflon tube with a rubber gasket in the syringe to inject 1 ml of styrene. The hydrogenation is carried out at intensive stirring, precluding the flow of process in the diffusion region. Control over the course of the process perform volumetric and GLC (a chromatograph Chrom-5, DIP, phase SE-30, the column length is 3.6 m, the temperature of thermostat 100°). The catalyst activity is 280 mol H2·(d) ATA Pd·min)-1that is, the quantitative conversion of styrene to ethylbenzene (table 1).

Examples 2-7: the Method is the same as in example 1. These examples illustrate the effect of the ratio P/Pd on the activity of the hydrogenation of styrene (table 1). The procedure for conducting experiments similar to example 1.

Table 1
The influence of the ratio P/Pd on the activity of the hydrogenation of styrene in the system Pd(acac)2 3< / br>
WithPd=1 mmol/l, [substrate]/Pd=870, the solvent is DMF, T=30°C, PH2=1 ATM
No.1234567
n00,10,30,40,50,71,0
Activity W, mol H2·(d) ATA Pd·min)-1249928015410921

Examples 8-11: these examples illustrate the effect of temperature recovery of Pd(Acac)2during the formation of the catalyst on the activity of the hydrogenation of styrene (table 2). The procedure for conducting experiments similar to example 1.

Table 2
The influence of the temperature of formation of the catalytic system Pd(acac)2+0,3 R on its activity in the hydrogenation of styrene

WithPd=1 mmol/l, [substrate]/Pd=870, the solvent is DMF, T=30°C, PH2=1 ATM
No.891011
A, K323343353363
Activity W, mol H2·(d) ATA Pd·min) 00290137

Examples 12-15: these examples illustrate the effect of the duration of the recovery process, Pd(Acac)2during the formation of the catalyst at optimum temperature (80° (C) on its activity in the hydrogenation of styrene (table 3). The procedure for conducting experiments similar to example 1.

Table 3
The influence of the duration of the process of formation of the catalytic system Pd(acac)2+0,3 P at 80°With activity in the hydrogenation of styrene WithPd=1 mmol/l, [substrate]/Pd=870, the solvent is DMF, T=30°C, PH2=1 ATM
No.12131415
Time min10253045
Activity W, mol H2·(d) ATA Pd·min)-10280222140

Examples 16-21: these examples illustrate the effect of the concentration of the catalyst on its catalytic activity (table 4).

Table 4
The effect of the concentration of palladium on the activity of the hydrogenation stir the La in the system Pd(acac) 2+0,3 P

the solvent is DMF, T=30°C (303 K), PH2=1 ATM, the volume of styrene = 1 ml
No.161718192021
The Pd concentration, mmol/l0,51,02,55,07,510,0
Activity W, mol H2·(d) ATA Pd·min)-1191280164333433

Examples 22-25: these examples illustrate the activity of the catalyst in the hydrogenation of various substrates (table 5). The procedure for conducting experiments similar to example 1.

Table 5
The activity of the catalytic system Pd(ASAS)2+0,3 PH3in the hydrogenation of various substrates WithPd=1 mmol/l, the solvent is DMF, the solution to 10 ml, T=30°C, PH2=1 ATM
No.22232425
SubstrateStyrenePhenylacetyleneNitrobenzeneBenzaldehyde
Activity W, mol H2·(d) ATA Pd·min)-1280156 12815
Quantity of substrate mmol9,07,32,59,9
Output products100% ethylbenzene100% ethylbenzene100% aniline90% benzyl alcohol

We offer palladium hydrogenation catalyst has high catalytic activity in the catalytic process under mild conditions (at room temperature and a hydrogen pressure of 1 barg. ATM).

1. Palladium hydrogenation catalyst containing the recovered compound of palladium and modifying additive, characterized in that as the source of palladium compounds using bis-acetylacetonate, palladium, and as a modifying additive white phosphorus (R4) in the following ratio of components: bis-acetylacetonate palladium/phosphorus = 1:0.1 to 1:1.

2. A method of obtaining a palladium hydrogenation catalyst according to claim 1, based on recovery of starting compound of palladium with hydrogen in the presence of the modifying additive, characterized in that as modifying additives used white phosphorus, which is injected to the stage of recovery of the compounds of palladium (II) hydrogen, and as the parent compound of palladium bis-acetylacetonate, palladium, at the optimum t is mperature the formation of catalytic systems 80-90° (353-363 K) and the optimal time of formation of the catalyst 25-30 minutes



 

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