PL161223B1 - Method for making butyl alcohol - Google Patents

Abstract

Method for producing butyl alcohol in a gaseous phase via catalytic hydrogenation with hydrogen a gas containing hydrogen, of a mixture of C4 aldehydes while the molar ratio of hydrogen to aldehyde is like 5.7- 61.4 / 1, at the temperature of 150-230 degrees C, under pressure of 0.1-1.0MPa, in the presence of a hydrogen activated catalyst , characterised in that the aldehyde C4 and hydrogen are continuously administered onto the catalyst bed at the velocity of 0.1-0.5l of aldehyde per 1 litre of the catalyst per hour, while the catalyst used in the process has 20-40% by weight of metallic copper, 2-8% metallic nickel and aluminosilicate 52-78% by weight, while aluminosilicate is a mixture composed of 75% by weight SiO2 and 25% by weight Al2O3.

Description

The present invention relates to a process for the production of butyl alcohols in the gas phase by catalytic hydrogenation of butyric aldehyde or isobutyraldehyde or a mixture thereof.

Known processes of hydrogenation of aliphatic aldehydes are carried out in the liquid or gas phase in the presence of various catalytic systems in a wide range of temperatures between 20 and 200 ° C and at a pressure of 0.1-5 MPa. The most commonly used catalysts are copper, nickel or copper-nickel with the addition of modifiers. French patent specification No. B5B 1B4 describes the hydrogenation of butyric aldehyde to butanol in the liquid phase using Raney nickel at a temperature of 20 ° C and a pressure of 0.1 MPa. In the group of nickel-magnesium catalysts for the hydrogenation of butyric aldehyde to butanol, according to the German patent specification No. 2,047,437, a catalyst with the composition of 29-31¼ by weight Ni, 6-8¼ by weight MgO and 25-27¼ by weight SiO2 was used. Using a temperature of 95C and 8.0 MPa, a butanol yield of 99.8¼ was obtained.

VJ in UK Patent No. 907,366 describes the hydrogenation of crotonaldehyde. The reaction was carried out in a tubular reactor filled to 1/5 part with a mixture of 5.64 by weight NiO and 50.34 by weight CuO on diatomaceous earth. The remaining 4/5 parts of the reactor were filled with 55.6 ¼ weight CuO and 1.5 ¼ weight alkali metal phosphate. Performing the process at 140 ° C, pure butanol was obtained from the condensate distillation with a yield of 99.8¼.

A similar method for hydrogenating crotonaldehyde to butanol is described in British Patent No. 906,527. A copper-nickel catalyst was used in the form of two separate, interconnected beds. 1/5 of the reactor was filled with catalyst containing 58¼ by weight Ni on diatomite, and the remaining 4/5 of the reactor with catalyst containing 55.6¼ by weight CuO and 1.5¼ by weight alkali metal phosphate on diatomite. The hydrogenation product contained less than 1¼ unreacted aldehydes.

In U.S. Patent No. 4,394,525, hydrogenation of C2-C20 aliphatic aldehydes was carried out at a pressure of 0.7 MPa, at a temperature of 50 * C, in the presence of a catalyst containing 3-60¼ by weight of Ni with the addition of metal oxides from the Ila group - Mg, Cu, Sr, Ba, or A ^ Cj, or aluminum phosphates. Under the conditions indicated above, the yield was about 68¼.

The essence of the invention consists in the use of C? Aldehydes in the hydrogenation process. in the mixture or of each separately modified copper-nickel catalyst.

The process according to the invention is such that the aldehydes C? in the gas phase and hydrogen in a molar ratio of hydrogen to aldehyde C ?, as 5,7-61,4: 1, administered in a manner of ^± n Continuously ^a catalyst bed with a speed of ^{± bj} E ^t -śclow ^{A 0,} l- ^0, 5 dcm? ^d uC ^{4 aldehydes per dcm of} catalyst per hour, at a pressure of 0.1-1.0 MPa, at a temperature of 150-230 ° C.

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A catalyst is used in the reaction, containing 20-40% by weight of metallic copper, 2-8% by weight of nickel and 52-78% by weight of aluminosilicate, the aluminosilicate being a mixture containing 75% by weight of SiOj and 25% by weight of AljOj. The use of the described catalyst in the process according to the invention allows to obtain a high conversion of aldehydes with high yield of butyl alcohols, with relatively mild temperature and pressure parameters. By carrying out the reaction according to the invention, a degree of aldehyde conversion of 99.5-100% is obtained.

^EXAMPLE 1 ⁵⁰⁰ cm3 were loaded into a tubular reactor with an inner diameter of 34 mm and a height of ^{1000 mm} . kataHza ^ ra ^g of furan ^l ac ^ji 3-5 mm. This carbonate was reduced with hydrogen at 250 ° C and 0.5 MPa pressure for 12 hours. The activated catalyst contained 30% by weight of copper, 2% by weight of Ni, 1% by weight of graphite and 67% by weight of an aluminosilicate containing 75% by weight of SiO and 25% by weight Al? Oj. The activated catalyst was fed continuously, dosing from the bottom of the reactor, at a temperature of 180 ° C, at a pressure of 1.0 MPa 0.31 / l ?.h of n-butyraldehyde and 20 Nl of hydrogen per minute (molar ratio of hydrogen to aldehyde 31.5 / 1). The product was collected at the top of the reactor; conversion of aldehyde to alcohol was 100%.

Example U. O. The reactor was charged and the catalyst was reactivated identically as in example 1. Then a mixture of aldehydes (50% wt. Butyric aldehyde + 50% wt. Isobutyraldehyde) was introduced in the amount of 0.2 l / l. H and 12 NLH.h./min. ( molar ratio H 6 / aldehyde = 28.4 / 1). At the temperature of 230 ° C and the pressure of 0.1 MPa, the degree of aldehyde conversion to butanol was 99.89%.

Example III. In the reactor, as in Example 1, the catalyst was charged and activated with hydrogen as in Example 1 to form a contact containing 20 wt.% Copper, 5 wt.% Nickel, and 75 wt.% Aluminosilicate, containing 75 wt. and 25% by weight Al {^^.

The activated catalyst was fed continuously, dosing from the bottom of the reactor, at a temperature of 150 ° C, at a pressure of 0.5 MPa, 0.50 1 / l ?.h of isobutyraldehyde and 6N1 hydrogen per minute (molar uodine / aldehyde ratio = 5 , 7/1). The product was collected at the top of the reactor. The conversion of isobutyraldehyde to isobutanol was 99.99%.

Example IV. A catalyst was charged to the reactor as in Example 1, which had been activated with hydrogen as in Example 1 to form a contact containing 40 wt.% Copper metal, 0 wt.% Nickel metal, and 52 wt.% Aluminosilicate, containing 75 wt.% S106. 1 25% by weight Al? Oj.

The activated catalyst was steeped continuously, from the bottom of the reactor, at a temperature of 170C, at a pressure of 0.1 MPa, 0.1 1 / l. H. Of a mixture of aldehydes (75% by weight of butyric aldehyde 1 25% by weight of isobutyraldehyde) 1 20 NI per minute of hydrogen gas containing 65 µl of hydrogen and 35 volume% nitrogen (61.4 / 1 molar ratio H H / aldehyde). The product was collected at the top of the reactor, containing 74.8 wt% butanol and 24.7 wt% isobutanol. The conversion of the aldehyde was 99.5%.

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Department of Publishing of the UP RP. Circulation of 90 copies. Price PLN 10,000

Claims (1)

Patent claim A method of producing butyl alcohols in the gas phase by catalytic hydrogenation of a mixture of aldehydes with hydrogen or a gas containing hydrogen, with a molar ratio of hydrogen to aldehyde, such as 5.7 - 61.4: 1, at a temperature of 150-230 * 0, under a pressure of 0.1 -1.0 MPa, in the presence of a hydrogen activated catalyst characterized in that the aldehyde C and hydrogen is fed continuously to the catalyst bed at a rate of 0.1-0.5 liters of aldehyde per liter of catalyst per hour, using a catalyst containing 20-40 by weight of metallic copper, 2-8 of metallic nickel and aluminosilicate in an amount of 52-78¼ by weight, the aluminosilicate being a mixture containing 75¼ by weight of SiO2 and 25¼ by weight ai ₂ ° ₃ . »« «