SU1055733A1 - Method for hydrogenating butyric anhydrides - Google Patents

Abstract

THE METHOD OF HYDROGENING OIL AL ;; EGIDS by treating with hydrogen into organic; solvent containing butyl alcohols, in the presence of a catalytic system, including a catalyst based on a leached nickel-titanium-aluminum alloy of the following composition, may.%: Nickel46-52 Titanium2-4 AluminumOther, at 100-210 ° C and volumetric rate feeds of 1-2 o tl and h ay and yc so that, in order to increase the yield of butyl alcohols, as the organic solvent is used the fraction of production of butyl alcohols with the maximum boiling point temperature of 120-260s of the following composition, wt.%: Butyl alcohols 10-15 Su-Alcohols С {о 17-22 (L Esters and hemiacetals of butyl alcohols Else, and as a catalytic system use a combination of two layer-by-layer catalysts based on highly alkaline copper — an aluminum alloy of the following composition, wt.%: Copper 45-55, aluminum 45-55 sd and nickel-titanium-aluminum alloy of reduced composition, taken at SP mass ratio

Description

The invention relates to the industry of organic synthesis and can be used for the preparation of butyl alcohols by the hydrogenation of butyric aldehydes. The known method of hydrogenation of molten aldehydes by treating the raw material with hydrogen in the presence of a catalyst based on - leached copper-aluminium or copper-chromium-aluminum-alloys at 100-250 ° C and a flow rate of the hearth. chi raw materials 0.4-0.6. The disadvantage of this method is the low removal of the target product per unit volume of the reactor. The closest to the invention in its technical essence and the achievable effect is the method of hydrogenating oily aldehydes by treating oily aldehydes with hydrogen in an organic solvent, butyl alcohol, in the presence of a catalytic system that is a catalyst based on leached nickel-titanium. - aluminum alloy, of the following composition, May.%: nickel 46-52, titanium 2-4, aluminium else, at 100-25. and the volumetric feed rate of the raw material is 0.5-2.0. The disadvantage of this method is not high enough butyl alcohol, amounting to 95-98% of the original oil aldehydes. The purpose of the invention is to increase the yield of butyl alcohols. This goal is achieved in that according to the method of hydrogenation of oily aldehydes by treatment with hydrogen in an organic solvent solution containing butyl alcohols in the presence of a catalytic system comprising a catalyst based on a leached nickel-titanium-aluminum alloy of the following composition, wt.%: Nickel 46-52, titanium 2-4, aluminum else, at 100-210 0 and flow rate of the raw material is 1-2 hours, characterized in that, in order to increase the yield of butyl alcohols, the organic fraction is used as an organic solvent. The properties of butyl alcohols with boiling points of 120-1 ° C boiling temperature of the following composition, wt.%: Butyl alcohols 10-15 Alcohols C (about 17-22 Esters and hemiacetals of butyl alcoholsEsalite and use a combination of two layer-based catalysts based on leached Copper-aluminum alloy of the following composition, wt.%: Copper45-55 Aluminum45-55 and a nickel-titanium-aluminum alloy of reduced composition, taken at a mass ratio (10-40): (БО-90. The use of the invention allows to increase the yield of butyl alcohols to 102-136 wt.% (Against 95-98% of the prototype). Due to the use of the catalytic composition of the two catalysts there is no destruction of the first in the course of the raw material of the catalyst layer of copper-aluminum alloy. In addition, the esters and hemiacetals of butyl alcohols are hydrogenated on the copper-containing catalyst, which gives an additional increase in the yield of butyl esters. For the proposed method, a fraction with boiling temperatures of 120–260 ° C is used, extracted from the bottoms of the production of butyl alcohols, produced by the method of propylene hydroforming to oil aldehydes, followed by hydrogenation of the latter to butyl alcohols on a catalyst based on leached nickel – titanium – aluminum alloy RIMER. In a flow-through laboratory reactor, 10 ml of a copper-aluminum alloy (50% A1 + 50% Cu) and 90 ml of a nickel-titanium-aluminum alloy (48% A1 + 49% Ni + 3% Ti) are loaded, and top and bottom alloys - ceramic Ariki. Leached with 40% aluminum with a 10% aqueous solution of alkali (NaOH) at 80l5 ° C for 6 hours. The resulting catalysts are washed with distilled water, pressed with nitrogen, reduced with hydrogen and at 20Q ° C with a hydrogen pressure of 200 atm. aldehyde 2.0 of hydrogen for 5000 h serves the raw mix containing 45% oil aldehydes and a fraction of 120–260 ° C composition: butyl sp.Irty 15, C – C17 alcohols, esters and poluacethly 68, isolated from the residue of butyl alcohols production. The product is analyzed on a YX-2 chromatograph with a thermal conductivity detector, the phase is a chromaton treated with PEG-20000, the temperature of the thermostat is 163 ° C, and the helium carrier gas. Due to the oil aldehyde, esters and hemiacetals, the yield of butyl alcohols to the initial oil aldehyde was 133%. The productivity of the reaction apparatus is 0.74 kg / h of butyl alcohols per 1 liter of the reactor volume.

The results of the hydrogenation of oil aldehydes, depending on the composition of the catalytic system and the solvent, are given in Table. 1 and 2.

The invention provides the use of VAT residue fraction 120-260 ° With the production of butyl alcohols, not previously used in the production of butyl alcohols. In addition, the operating conditions of the hydrogenation unit are improved, and the productivity is increased.

units of the volume of the reaction apparatus as a result of the replacement of an inert diluent (butanol) with a fraction isolated from the bottoms of the production of butyl alcohols, containing raw materials (0.5b 0, 74 kg / h of butyl alcohols per 1 liter of reactor volume). Along with butyl alcohols, a clear distillation isolated the alcohol fraction with a yield of 25%. Kotor can be used to obtain a plasticizer of grade DAF-789.

.Table 1

Catalyst (2):

49

49

nickel

49

49

49

49 Volume velocity, 2.0 2.0 2.0 Temperature, from 200 200 200

Butyl outlet

134

134 alcohols, wt.%

Continued table. one,

136

83

115

65 1.0 2.5 2.0 2.0 200 200 100 210

Claims (1)

METHOD FOR OIL ALDEHYDE HYDROGENATION by treatment with hydrogen in an organic solvent containing butyl alcohols in the presence of a catalytic system comprising a catalyst based on a leached nickel-titanium aluminum alloy of the following. composition, wt.%: Nickel 46-52 Titanium 2-4 Aluminum The rest, at 10-210 ° C and. the volumetric feed rate of 1-2 h '/' of t l and the fact that, in order to increase the yield of butyl alcohols, the fraction of the production of butyl alcohols with boiling points of 120-260 ° C of the following composition, wt. %: Butyl alcohols 10-15 Alcohols Su — C "j 17-22 Esters and hemiacetals of butyl alcohols The rest, and as a catalytic system, a combination of two layer-by-layer catalysts based on highly alkaline copper - aluminum alloy, of the following composition, wt.%: Copper 45-55, aluminum 45-55 and nickel - titanium-aluminum alloy of the reduced composition taken at mass ratio (10-40): (60-90). IWTTiS>