CS211004B1 - Preparation method of nickel catalyst on the carrier for selective hydrogenizations - Google Patents

Description

BACKGROUND OF THE INVENTION The present invention relates to a process for preparing a supported nickel catalyst, particularly suitable for use in the preparation of a supported nickel catalyst. selective hydrogenation of polyunsaturated organic compounds to di- or mono-unsaturated compounds.

Nickel catalysts, such as silica, aluminum, silica gel, and the like, are among the longest and most commonly used heterogeneous catalysts in practice. A number of processes have been proposed for the preparation of which the catalytic active mass is formed by stoning and reducing the starting nickel hydroxide or basic nickel hydroxide, which is obtained by precipitation of nickel salts with hydroxides or by cyclic treatment. It is also recommended to moodify the catalyst with some metals, such as Cu, Ag, Cr, Zr, Th, Sn, Re, and metals VIII, to increase the acacavity and the seecurity. groups of the periodic system.

A detailed study has shown that the ietetkivitl and the kkiivity of the nickel catalyst can be increased if some of the hydroxyl groups of the layered structure of the lowland hydroxide and / or the basic nickel carbonate are nailed during the preparation of the catalyst by anion (ВИ ₄ > Based on this finding The present invention is directed to a process for preparing a supported nickel catalyst for the selective hydrogenation of saturated or unsaturated organic compounds to di- or mono-monosubstituted compounds by precipitation of the nickel salt on the support with alkali. a process in which the obtained nickel hydroxide and / or basic alkali metal with a composition of NiCO 3 x Ni (OH) g. y HgO, where x is 1 to ³⁰ and у is any number, is treated for ⁵ up to ⁶⁰ minutes at a temperature of from ²⁰ to ¹⁰⁰ ° C and at a pH of more than 10 at a temperature of 0.005 to 1.25 m. ol / mole Ni. promyye resulting mass is dried and · after adjustment to the desired grain size is reduced at ^{250 F} and ⁴⁸⁰ ° ^C until the degree ^of reduction · ^0.40 and ^from 0.99. The effect of the inventive totatysator can be enhanced by treating the lithium hydroxide and / or alkaline carbonate together with the addition of Cu, Ag, Cr, Zr, Th, Sn, Re or Rectal Metal VIII salts. groups in the periodic system in an amount of 0.1 · to 10%.

Due to the action of alkaline bonlhydrides. In the solution o and the precipitate obtained by mixing a solution of some soluble acidic acid with the appropriate alkali, some hydroxyl groups are exchanged in the surface layers of the structure of the lithium hydroxide and / or basic carbonate of the acidic anilne. (BH ^) '. The resulting catalyst exhibits some of the higher titers and ethers for the hydration of polyunsaturated organic compounds and di- or monounsaturated compounds. ,

The following are examples of embodiments of the process of the invention.

He did

To a heated solution of soda with stirring influx ^ Oa iilikígtLu suspension in a solution of sulphate of Elne ^ ^p ^ s ⁹⁵ ° C. ^S r ^until measurement was completed the solution hydrlxid ^l solution in such an amount that the molar ratio of nickel alkáHí · k · 2 was: 1st The precipitate obtained, which, after filtration, sieving and drying, had a NCO 3 content of 1 °> 5 NHOH. 7 HgO was treated with a 10% aqueous solution of sodium borohydride (pH = 10) for 60 minutes at pH = 10.5. Thereafter, the precipitate was filtered, washed three times with methanol and, after drying, reduced at 260 ° C to 280 ° C for 10 hours. The catalyst thus prepared exhibited a significantly higher selectivity in the liquid phase hydrogenation of cyclolktadieol than the catalyst obtained in a similar manner in which the precipitate of basic alkali metal was not exposed to sodium. The cuvanitative results, including the hydrogenic conditions, are shown in the attached Table 1.

Example 2

The procedure of Example 1 was followed except that a nickel nitrate solution containing 10% silver nitrate was precipitated. The catalyst obtained by reducing the sample at ⁵⁰ ° C for 3 tulle 3krét actively and 2,8krét.selektivnější hydrogenation cyklododekehrienu cyklodecen than on the same sample, not devoid íorohyddidu sodium bicarbonate.

He said a d 3

A slurry of silica in a nickel (II) chloride solution containing ^0.1 % PdCl ^{g was} charged to the precipitation vessel and ^, at a temperature of ⁹⁸ ° C, this precipitated the alkali to nickel carbonate through sodium at 2.1 moles. per mole of nickel. To a suspension in the mother liquor occiput then added 0.01 mol% íorohydridu solution and extracted at pH 13.7 Tyl stirred for 10 ^minutes at ⁹⁸ ° C ri. After Filiač, washing and ^y of drying tulle katal ^{characterized Tor} redukovd s ^p 45 ^{0 p} l to ^some growth reduction of 0.85. Seeeetivita resulting catalyst for tydrogenaci c ^y klooktadienu for cyclo-. octenes increased 3.1 times as a result of treatment with sodium borohydride.

Example 4

Nickel nitrate solution, a content of the JCI thermally stable oxidic carrier, tulle 3 precipitation at ⁰ ° C with ^d · tyďroxidem Nym in rnožžWí ^1, 5 moles to 1 mole of ni ^ u. Z ^ kara tydroxid suspension is mixed with nickel Tyl rozookem íorohydridu solution (0.6 moles per 1 .mol-nickel) and zaltflvda ^p 7 s ⁰ to ⁸⁰ ° C for ⁶⁰ minutes. After filtration ^, filtration ^, reduction and reduction to a degree of reduction of 0.63, the catalyst showed a 5.3 times higher scavenger than a similar sample, untreated with borohydride.

Table I

Comparison of the hydrogenation of the cyclization with the catalyst prepared according to Example 1 (Catalyst A) and with the catalyst prepared by the process without the action of sodium (Catalyst B).

_o 5

Reaction conditions: temperature 30 l; hydrogen pressure 1.0374.10 Pa; catalyst concentration 0.833 g

nickel per 1 liter reaction mixture; solvent n-heptane. time CATALYST AND CATALYZER 'B (min) concentration is an individual component (moo / 1. 10 ”‘) D M P D M P 0 5.44 0 0 5.38 0 0 5 3.38 1, 96 0.04 4,56 0.77 0.05 10 1, 84 3.38 0.11 3.90 1.31 0.18 20 May 0.32 4,56 0.50 2.84 1, 97 0.55 30 0.03 4.36 1, 02 2.10 2.23 1, 01 40 0 3.88 1, 54 1, 59 2.28 1, 48 50 0 3.40 2.02 1.18 2.21 1, 98 70 0 2.58 2.86 0.67 1, 85 2.84 90 0 1.92 3.50 0.36 1, 44 3.54 110 0 1.42 4.04 0.21 1.10 4.06 130 0 1, 02 4.44 0.13 0.78 . 4.48 150 0 0.72 4.72 0.06 0.56 4.75

D = cyclic M = cyclooctene

P = ^ k ^ octane

Claims (2)

SUBJECT OF THE INVENTION A process for the preparation of a supported nickel catalyst for the selective hydrogenation of polyunsaturated organic compounds onto di- or monounsaturated compounds by precipitation of a nickel salt on a supported alkali, characterized in that the nickel hydroxide and / or basic nickel carbonate of NiCO 3 x Ni (OH ·) 2 «У ^{where x 1} to 30 а у is an arbitrary number, treated at a temperature of 20 to 100 ° C and at a pH of more than 10 for 5 to 60 minutes with an alkali borohydride solution of 0,005 to 1,25 mol per 1 mol of nickel, after which the mass obtained is washed, dried and after adjustment to the desired grain size reduced at 250 to 480 ° C to a reduction degree of 0.40 to 0.99. 2. Process according to claim 1, characterized in that the nickel hydroxide and / or the basic nickel carbonate is treated together with the addition of copper, silver, chromium, zirconium, thorium, tin, rhenium or a metal of VIII. % of the periodic system in an amount of 0.1 to 10%.