SU1426631A1 - Catalyst for oxidizing methanol to methylformate and method of producing same - Google Patents

Abstract

The invention relates to catalytic chemistry, in particular the preparation of a catalyst (QD) for the oxidation of methanol to methyl formate (MP), an intermediate product for the synthesis of dimethylformamide. To simplify the process and increase the activity of QD based on palladium, 1,10-phenanthroline is introduced into it in a molar ratio of (15-3): 1, dissolved in methanol and treated with hydrogen. CT contains 62–90 wt.% Palladium and the rest 1, U-phenanthroline. When methanol is oxidized in the presence of CT, MF process performance from 1 liter of reaction volume to 200 g / h is ensured. CT activity of the air “will grow 8-12 times 2 SEC ,, f-ly, 1 scoreboard

Description

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This invention relates to homogeneous catalysts for the oxidation of NOL in methyl form.

Methyl formag is an important polymer, organic synthesis, and is used to produce formic acid and dimethylformamide,

 of the invention is to increase the activity and selectivity of the catalyst and simplify the method of preparation of

The invention is illustrated by the following examples.

Example 1 Catalyst Preparation Procedure

 g (0,009 mol) acetate palla

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DAYS and Oe2 g (OjOOl mol) 5,10-phenanthroline (phen) is dissolved in 250 ml of methanolo. The molar ratio of the acetates-pagshad (P) to 1, 1 is O-phenanthroline; 9 hydrogen at 20 ° C and 1 atm with continuous stirring for 30 minutes. The reactor is then purged with nitrogen and methanol is distilled off in a stream of nitrogen.

Polucha5ot 1.0 g of catalyst - (quantitative code) „

The catalyst is a dark-brown substance, soluble in methanol, acetic acid, acetonitrile. According to the elemental analysis data, a catalyst is obtained, containing% by mass%: Palladium 82.6

1 r Yu- -Fanantro - LIN17 5 4

It is more convenient to use a catalyst, but in a methanol solution, in which, it is obtained, it is not necessary for Tvvво to separate it from the mother liquor. Thus, the catalyst can be directly burned in the methanol oxidation reactor to methyl formate,

Example 2 Oxidation of methanol to methyl formate under the action of the proposed catalyst

50 ml of methanol J containing 1.8 g of catalyst are placed in a thermostated reactor flow through the catalyst. The content of the catalyst in the reaction mixture is 36 g / l. The catalyst contains 82.6% by weight of liquid and 10% phenanthroline. The temperature in the reactor is up to and the flow through the reactor oxygen at a speed of 30 l / h over the same research institute 3 hours

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The concentration of methanol oxidation reaction products was determined by gas chromatography: methyl formate — column 200–0.3 cm, 10% nonyl phthalate on chromatone, carbon dioxide and WATER — column 2500.3 cm, polysorb-1. The yield of methyl formate is 30.9 g (0.51 mol), carbon dioxide - 1.35 g (0.03 mol). Methanol conversion 84.3%. According to the analysis and material balance, formaldehyde and formic acid are not formed. The selectivity of methanol to methyl formate is 97.1%.

Removal of methyl formate from 1 liter of reaction volume is equal to 206 g / Cho Removal of methyl formate from 1 g of catalyst is 5.72 g / h

The table shows data on the effect of the ratio of palladium and 1,10-phenanthroline in the catalyst on its activity and selectivity.

A catalyst with different contents of palladium and 1,10-phenanthroline was prepared according to example 1 by changing the initial ratio of palladium acetate (P) and 1,10-phenanthroline. Catalyst loading is 0.6 g. Oxygen supply rate 10 l / Cho Temperature in reactor 50 From 10 hours reaction time

Thus, the proposed catalyst has an activity of 8-12 times the activity of the catalyst of the prototype. Removal of methyl formate from 1 liter of reaction volume reaches 200 g / Cho

The use of the proposed method for the oxidation of methanol to methyl formate allows one to avoid the use of scarce formic acid and costly corrosion-resistant equipment (in the case of esterification) or to significantly reduce capital and energy costs (in the case of carbonylation of methanol).

Claims (2)

Invention Formula 1o Catalyst for the oxidation of meth "nola" methyl formate based on palladium, characterized in that, in order to increase the activity and selectivity of the catalyst, it additionally contains 1S10-phenanthroline  1426631 - with the following content of components u and so that, in order to simplify the maCo%: no method of preparation of the catalyst Palladium62-90 1,10-lenaitro LIN Rest 2. A method for preparing a catalyst for the oxidation of methanol to a palladium-based methyl formate, distinguishes and obtaining a catalyst with increased activity and selectivity, palladium acetate and 1,10-phenanthroline are taken in a molar ratio of (15-3): 1 and dissolved in methanol, the resulting solution is treated with hydrogen and obtaining a catalyst with increased activity and selectivity, palladium acetate and 1,10-phenanthroline are taken in a molar ratio of (15-3): 1 and dissolved in methanol, the resulting solution is treated with hydrogen