SU932692A1 - Method for preparing catalyst for selective hydrogenation of acetylene compounds - Google Patents

Abstract

A METHOD FOR OBTAINING A CATALYST FOR THE ELECTORAL HYDROGENATION OF ACETYLENE COMPOUNDS By treating a solution of the complex compound of palladium in an organic solvent with a compound with a triple C-C bond, which is characterized by the fact that, in order to obtain a catalyst with increased ac activity, as a complex compound, it will be removed. (P) or bis- (dibenzylidene acetone palladium (O) and, as a compound with a triple C – C bond, a hydrogenated compound or proparicol alcohol. (L

Description

with so you and so with

The invention relates to organic synthesis and relates to the homogeneous catalysis of the hydrogenation of acetylene compounds into ethylene and can be used, for example, in the purification of olefins from acetylene and its derivatives.

A known catalyst for the selective hydrogenation of acetylenic compounds into ethylene in mild reaction conditions, which are rhodi 1.1 complex compounds.

The disadvantage of this catalyst is its high cost.

The closest in technical essence and the achieved effect is a method for preparing a catalyst for selectively hydrogenating acetylenic compounds by forming a solution of a palladium complex compound, using bis- (triphenylphosphine} palladium dichloride), in an organic solvent - ethanol, an aromatic hydrocarbon, dimethylformade, a compound with a triple C – C bond, which uses hydrogenated compound 2.

A disadvantage of the known method is the preparation of a catalyst with low activity. In particular, in the case of hydrogenation, the acetylenic compounds {dimethylethynylcarbinol and hexin-1) the hydrogen uptake rate is 0.2-0.5 ml per (lol of the catalyst or 19-47 ml min.

The aim of the invention is to obtain a catalyst with increased activity.

This goal is achieved by a method of preparing a catalyst for the hydrogenation of acetylenic compounds by treating a solution of the palladium complex compound in an organic solvent with a compound with a triple C – C bond, which uses a hydrogenated compound or propargyl alcohol. At the same time, palladium carboxylate (Q) or bis (dibenzyldecacetone / palladium (O)) is used as the palladium complex compound. Dimethyl sulfoxide, dimethyl forms / 1, and -hexane, toluene, chlorobenzene, methyl ethyl ketone dioxane or tetrahydrofluoride can be used as the organic solvent. .

The advantage of the present invention is to obtain a catalyst with increased activity. Thus, in the process of hydrogenation of acetylenic compounds, the rate of hydrogen absorption increases to 1.0-2.0 ml or 370-500 ml with identical methods known, i.e., e, almost a hundred times higher than by a known method.

The catalyst is prepared as follows: palladium carboxylate (ij) is dissolved or palladium complex (O with dibenzylidone-acetone in an organic solvent, the compound with acetylene bonds (for example, phenylacetylene, propargyl alcohol, etc., is introduced into the solution) and kept in an inert atmosphere 10 - 15 min. The resulting catalyst solution is used to carry out hydrogenation. The best results are obtained when using as a component containing acetylene bonds, the same substance directly, which is subject to hydriars Some of it in this case will be spent on the formation of a katashi.,

Example: 10 mg of bis- (dibenzylideneacetone / palladium (1 ,, 0.8 g of diphenylacetylene (4,) and 10 ml of dimethyl sulfoxide) are charged to the reactor. The mixture is stirred for 15 minutes under nitrogen atmosphere, then nitrogen is gated for hydrogen. fv; j pressure of hydrogen is atmospheric. Achieved hydrogen absorption rate is 2 ml / min. After that, 1 mol H. per 1 mol of diphenyl acetyl. foam reaction almost ceased. Reaction product — diphen-1: polyethylene — identified by method. resonance.) The course is close to 100% ,,..

EXAMPLE 2 A palladium compound, solvent, phenylacetylene are loaded into the reactor (the quantities of components are given in Table 1, the mixture is stirred for 10 minutes under nitrogen atmosphere, then the nitrogen is replaced with hydrogen, and Pei is stopped after the absorption 1 1 mol H2 per 1 mol phenylacetylene, In all cases, the reaction product is styrene, identified by gas-liquid chromatography. Yield 95 - 98%, Hydrogenation of phenylacetylene at 20 ° C and atmospheric pressure.

1.7-10 dimethyl sulfoxide

idenadi

The same Chlorobenzene Methyl ethyl ketone Dimethylformamide

| 1

Dioxane

Tetrahydrofuran

 and

H-Hexane Toluene 2,2-10 Dimethyl sulfoxide The same Toluene Dimethylformamide

2,2-10- Dimethyl sulfoxide

PdCC HgCOOlj Prize. 10 mg of bis- (dibenzylideuacetone) palladium, 9 ml of toluene and 1 ml of hexin-1 are loaded into the reactor. The mixture was stirred for 10 minutes under a nitrogen atmosphere, then the nitrogen was replaced with hydrogen. Reaction temperature 20s, hydrogen pressure is atmospheric. Hydrogen uptake rate L / 1.5 ml 2 / min. The reaction product is hexane - 1 yield 96%. EXAMPLE 4 10 mg of bis- (dibenzylideneacetone 1 palladium, 9.4 mp dimethyl sulfoxide and 0.6 ml of propargyl alcohol) are charged to the reactor. The mixture is stirred for 10 minutes under a nitrogen atmosphere at room temperature. The temperature is then raised to and the nitrogen is replaced with hydrogen. The average hydrogenation rate is L / 1 ml H 2 / min. The main reaction product is llyl alcohol,

4.1-100, 61

3.1- SW

About the same 3.7-10- - 4.810-2, 8 10-3 11 4.5- 10

 and 4, b-1SG

. m 3.1-10.

, -3

3.4-10

0.45 3.8-10-3

about the same

, -3 11

4.0-10

gz

3.7-10

identified by chromatography. Yield 93%. EXAMPLE 5 0.005 g (8.7 10- ° M) bis (dibenzylibenacetone) palladium, dimethyl sulfoxide and propargyl alcohol are introduced into the reactor. The total volume of the solution in the reactor is 10 ml (the amount of propagglyl alcohol added is given in Table 2. The mixture is stirred for 15 minutes under a nitrogen atmosphere, then the substance to be hydrogenated is added, the nitrogen is replaced with hydrogen and the solution is hydrogenated at 20 ° C and the atmospheric pressure of hydrogen. The reaction rate is estimated by the time needed to absorb 1 mol H in terms of the amount of compound to be hydrogenated. The analysis of the products is carried out in the same way as in Examples 1 and 2. The results of the experiments are shown in Table 2.

79326928

 For Comparison in the same table of the torus is 15 min. experiments on hydrogenation are carried out, when the intermediate winding is catalyzed by mediocre hydration.

Claims (1)

METHOD FOR PRODUCING A CATALYST FOR SELECTIVE HYDROGENING ACETYLENE COMPOUNDS by treating a solution of a palladium complex compound in an organic solvent with a compound with a C — C bond, characterized in that, to obtain a catalyst with increased activity, palladium carboxylate or P (p) is used as a complex compound (P) bis- (dibenei.lidenacetone 1 palladium (0) and, as a compound with a triple CC bond, a hydrogenated compound or propargyl alcohol, Q <q ω s © GO