SU601042A1 - Method of preparing a skeleton catalyst for hydrogenating unsaturated organic compounds - Google Patents

Description

In the range of 30–300 ° C, the intermetallic gallium phase is formed with this metal (for example, Ni Ga), which, like excess x ally, is easily leached with an alkali solution, for example, with a 20% solution of potassium hydroxide (KOH),

The proposed method allows to obtain catalysts from all metals of the VIM group of the periodic table of elements. VIM group metals can be used both in powder form and in the form of products of complex configuration, for example, in the form of pipe plates.

The invention is illustrated by the following examples.

Example. In china

a 0.5 liter cup is placed 1.25 mg of gallium and melted at 30 ° C. 250 mg of powdered carbonyl nickel in a ratio of (/ V / fra 2: 1) are powdered with liquid gallium and rubbed with a pestle for 1-0 minutes until a homogeneous mass is formed. 50 ml of a 20% KOH solution are poured in and 20 g of potassium are added to the mixture for 20 minutes. The resulting catalyst is washed with distilled water until a negative reaction is made to K and OH ions. The washed catalyst is transferred to a reaction vessel, a duck, saturated with hydrogen and hydrogenated with potassium maleate (MKK) or 0.22 ml of dimethylethynylcarbinol (DMEK); 0.1N solution KOH at 40 ° C. The results of the experiments: software Hydrir The figures are given in table.

Example2. 250 mg of carbonyl nickel and 250 mg (or 1250 mg) of liquid gallium in a ratio are placed in a porcelain bowl; 1jl or 1: 5 and grind for 10 minutes. The cup is transferred to an oven heated to 100-150 ° with a ratio of components (Ni: 5a) of 1: 1 or 300 ° C at a ratio of 1: 5 and held for 2-3 hours. Then cooled and subjected to Kisefouling The catalyst was washed and hydrogenated as in Example 1. The results were hydrogenated.

is given in table.

 Example ZB. Two porcelain cups are placed on 125 mg of nopouiKOoe of different scallate nickel obtained by thermal decomposition. and 1250 and 625 mg of gallium (in a ratio of 1:10 and 1: 5), heated to 30 ° C and stirred until homogeneous.

In the first cup containing the mixture, nickel and gallium (Hi: Qa ratio 1:10), after 10 mi, 50 ml of a 20% KOH solution are poured and gallium is leached.

The second cup (Ni: Go ratio 1: 5) is transferred to the closet and

heated at 300 ° C for three hours. Cooled to room temperature, the mixture is leached with a 20% KOH solution. Washing the catalysts obtained by leaching both in the first and in the. in the second case, produced as in Example 1.

Maleate Hydrogenation Results

potassium and dimethylethylene on these catalysts are given in table.

Example4. In the porcelain cup; 250 mg of electrolytic nickel powder and 250 mg of gallium (Ni ratio; Gd; i: l) are placed, heated to and triturated. After 10 minutes of rubbing and obtaining a homogeneous mass, 50 ml of a 20% KOH solution are poured into a cup, heated to boiling and leached.

Leached catalyst is washed. and transferred to a catalytic duck in which hydrogenation is carried out. The test results are shown in Table.

Example 5. A nickel porous plate (total porosity 70A) with a thickness of 0.5 N1M, weight 125 mg is placed in a porcelain dish, moistened with liquid gallium (ratio Ж: Qa

Is3), heated to and maintained for 3-4 hours. The cooled plate is shot (0.5-1 mm) and leached with a 20% solution of KOH at 97 ° C. Nickel-waded plates, blackened on both sides, are washed and transferred to a catalytic duck, saturated with hydrogen, and hydrogenated with ICC and DMEK in 0.1 n KOH solution at 40 ° C.

The results of the experiments are given in Table.

. EXAMPLE 6. Industrial refined palladium wafer plates (rhodium, ruthenium, and iridium — 250 mg each), passive in hydrogenation reactions, are placed in a porcelain dish. 1250 mg (in each separate case) of metallic gallium (platinum metal: gallium is 1: 5 in ratio) and heated to AOC are introduced into it.

Molten gallium and the corresponding platinum-group metal are mixed and triturated to form a pasty mass. The cup with the contents is transferred to an oven, heated to 300 ° C and held for 3-5 hours.

50 mp of a 20% KOH solution are poured into the cooled cup, heated to boiling and gallium is leached for 20 minutes.

The catalysts thus obtained are washed out and transferred to a catalytic weft to determine their activity. In hydrogenation reactions

potassium maleate and dimethylethynylcarbinol under the conditions described above. The test results are shown in Table.

Example. In accordance with Example 2, catalysts are prepared from powdered cobalt and iron.

The results of experiments on the hydrogenation of the ICC and CMEC

in 0.1 N. solution of KOH when activated

on the proposed method of metallic materials

(at Co: Ga ratio of 1: 3, ь and Fe: GiQii: 5) and their activity in the reaction of potassium maleate hydrogenation of dimethylethynyl carbinol is tested. The test results are shown in Table.

Table

It follows from the table that all the studied powders and the nickel porous plate are activated by the offer by the method 4 at both low and high temperatures. A nickel catalyst prepared by treating inactive powders (carbon-gel, oxalate, and electrolytic) with liquid gallium is hydrogenated by potassium maleate and dimethylethynylcarbinol at a rate of 100, 170, and 180 ml / min. Under similar conditions, the rate of hydrogenation of the ICC on the Rene skeletal catalyst is as low as 40 ml / min per 1 g. These comparisons indicate one of the significant advantages of the proposed method to compare with the previously known one. However, considering that Rene nickel is prepared by fusing nickel with aluminum at temperatures above 1000 ° C, followed by grinding, dispersion into fractions and long leaching, other equally important advantages of the nickel catalyst prepared by the proposed method become apparent. In particular, the ready-made insstte powders produced by the industry are used as feedstock for the preparation of the catalyst. After their treatment with gallium, the nickel particles stick together, but do not rbrazuyut solid monolithic ingots and, unlike the Ki-Av alloy, they do not need to be ground.

Platinoid powders, like nickel, are activated by the proposed method. By activity, the catalysts are located in the range: in the case of HM3K-Pa Ru HtJ Pt 3f, eft case.

Thus, the activatrix is more exposed to the refined ruthenium powder, to a lesser platinum and iridium.

From a practical point of view, of particular interest is the activation of a nickel porous plate, which is widely used in fuel cell electrodes, in terms of 1 g of metal, its activity is quite high, Tin, as is well known, can be given any shape. This may contribute to the use of activated sheet in the processes of hydrogenation, hydrogenolysis, oxidation of various organic compounds.

Thus, the proposed method for the preparation of catalysts of the metals of the MIfl group is simple and differs in significant novelty compared with previously known methods. The usefulness of the method is also obvious: the activity of nickel catalysts is more than 4 times higher than the widely known catalysts for Rene nickel.

In addition, the proposed activation method, in contrast to the known methods, makes it possible to impart catalytic properties to products of complex configuration (plates, powders, pipes, and porous materials). The activation of materials is carried out at relatively low temperatures.

Claims (2)

1. Theological B, M., Kazakova Z.S. Skeletal catalysts, their properties and use in organic chemistry. M., Toshimizdat, 1957, p. 7-11. 2.C.P.Nach.J.Amer.Chem: Soc-, 1960, 82, 6203.