DE1953263A1 - Process for the preparation of amines from alcohols - Google Patents

Description

Badische Anilin- & Soda-Pabrik AG

Our reference: ■ 0.Z. 26 439 Schs / Pj 6700 Ludwigshafen, October 22. 1969

Process for the preparation of amines from alcohols

From the English patent specification 679 014 and the American patent specification 3 022 3 ^ 9 it is known to amines by reacting Manufacture alcohols with ammonia over copper catalysts. However, the implementation is very incomplete and limited to the Part of a post-amination over a nickel catalyst. In addition, dialkylamines are predominantly formed. ■

According to another in American Patent 3,151 The process described uses catalysts made of nickel, cobalt, copper, manganese, chromium, molybdenum and thorium for the production of amines and polyamines. The disadvantage of this process is the high proportion of N-disubstituted amines in the amines formed Amines. For example, ethanolamine is produced alongside Ethylenediamine is a significant proportion of undesirable piperazine. The same applies to the German interpretative document 1 170 960 too, where Raney nickel was used as a catalyst will.

It is also known from British patent specification 833 589, oxides of nickel, cobalt or copper or their mixtures to be used as catalysts in the production of amines from alcohols. This method has the disadvantage that a great deal Piperazine is formed and very high temperatures are necessary.

It has now been found that one can convert alcohols by reaction with ammonia or amines in the presence of hydrogen and a cobalt, Nickel or copper-containing catalyst, the corresponding amines are obtained in very good yield if the reaction is carried out in the presence a catalyst which, based on the metal content of the catalyst, is 70 to 95 percent by weight of a mixture

209808 / 19B7

Ί953263

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contains cobalt and nickel and 5 to 30 percent by weight copper, the weight ratio of cobalt to nickel being 4: 1 to 1: 4.

The cobalt to nickel weight ratio of 2: 1 to 1: 2, in particular 1: 1 and a copper content of 10 to is preferred 20 percent by weight, in particular 15 percent by weight in the catalyst.

The catalyst used in the process of the invention can also contain up to two of the metals manganese, chromium, zinc, vanadium or silver.

It can optionally also phosphoric acid or boric acid or their mixture or the corresponding oxides or their salts or Contain alkali metals, e.g. sodium or potassium, or alkaline earth metals, e.g. calcium or barium.

The abovementioned metals or acids optionally present in the catalyst in addition to cobalt, nickel and copper can be used in Quantities up to 20 percent by weight, based on the metal content of the catalyst, expediently up to 10 percent by weight, in particular 1 to 2 percent by weight, present in the catalyst.

The reaction between alcohol and ammonia or amine takes place in the presence of hydrogen, optionally in the presence of water, at one temp
of at least 10 atm.

Water, at a temperature of 100 to 250 ° C under pressure

Alcohols, e.g. ethanol, propanol, butanol, pentanol, hexanol, 2-ethylhexanol, tridecanol, stearyl alcohol are suitable as starting materials and cyclohexanol, also alkanolamines, e.g. sthanolamine, Propanolamine, isopropanolamine, hexanolamine, diethanolamine, diisopropanolamine or polyalcohols, e.g. ethylene glycol, propylene glycol, butanediol, pentanediol, hexanediol, 4,4'-bishydroxycyclohexylpropane- (2,2), or glycol ethers, e.g. methyl glycol, ethyl glycol, butyl glycol or polyalkylene glycol ethers, e.g. polyethylene glycol ether, Polypropylene glycol ether and polybutylene glycol ether. _,

209808/1957

SAO ORIGINAL

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If ammonia is used as the second reactant, it is obtained one primary amines. You can also use primary amines as reactants, then secondary amines are obtained. at If secondary amines are used, tertiary amines are obtained accordingly. Suitable amines are, for example: methylamine, dimethylamine, Ethylamine, diethylamine, propylamine, butylamine, amylamine, Hexylamine, cyclohexylamine, ammonia or the amines are used in a stoichiometric excess, based on the alcohol. Preference is given to more than 5 moles, suitably more than 10 moles, in particular 20 to 30 moles, of ammonia or amine per mole to be introduced Amino group applied. The hydrogen is in a Amount of 5 to 100 liters per mole of alcohol component, in particular 10 to 50 liters per mole of starting material.

The process according to the invention can also be carried out in the presence of water, e.g. 1 to 50 percent by weight, based on the alcohol component, be performed.

The catalyst is applied to a carrier, for example aluminum oxide or silicon dioxide. The metal content of the catalysts is expediently 5 to 80 percent by weight, in particular 10 to 30 percent by weight, based on the total catalyst.

Copper and the cobalt / nickel mixture are expediently present in the catalyst in a weight ratio of 1:20 to 1: 3. The remaining Metals manganese, chromium, silver, zinc, vanadium or the acids phosphoric acid or boric acid or the alkali metals sodium or potassium or the alkaline earth metals calcium or barium in the catalyst are expediently in a weight ratio of 1: 200 to 1:10 the cobalt / nickel mixture.

The catalysts can be prepared, for example, by adding the metal components, if appropriate together with the aforementioned Acids or their salts by themselves or on a powdered carrier from their salts in aqueous solution, e.g. with sodium carbonate or sodium hydroxide, falls or the precipitation applies to such a carrier, the neutral washed mass at increased Temperature, e.g. at temperatures from 60 to 180 ° C, dry

-4-209808 / 1957

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net and then the mass pressed into shaped bodies, such as pills or strands, is heated for some time to an elevated temperature, such as 300 to 800 ° C., in the muffle furnace. Instead of the acids mentioned or their salts, it is also possible to use acids or their salts which convert into pyro- or polyacids or their salts on heating, for example phosphoric acid. Contacting the catalyst with hydrogen, preferably at temperatures of 220 to 300 ⁰ C, reduced before use.

Other cobalt, nickel and copper-containing catalysts are obtained for example, when aqueous solutions of the nitrates of cobalt, nickel, copper, and possibly also of the metals mentioned Ψ and inorganic acids or salts thereof are added to the preformed solid support and subsequently the Tränkkontakt so obtained 300 to 800 ° C heated in the muffle furnace.

The reaction of alcohol and ammonia or amine can be done without Lö solvents are carried out. However, it can be advantageous to use the reaction discharge as the solvent.

The method according to the invention can be carried out batchwise will. It is advantageous to work continuously in technology. This working method is described here, for example: A vertical upright high-pressure pipe, which is filled with a catalyst of the composition mentioned, is from above with a Mixture of the alcohols mentioned and ammonia or amines in the specified ratio and recycled reaction discharge loaded. (The high-pressure pipe can also be fed hydraulically from the bottom to the top.). At the same time, one doses hydrogen to. The hydrogen is advantageously circulated, enriched with ammonia. The described values are kept during the reaction Pressure and temperature conditions. From the reaction discharge, after it has been freed from ammonia or amines, through fractional distillation isolates the desired amines.

The amines obtainable by the process according to the invention are suitable for the production of emulsifiers and pesticides,

-5-209808 / 1957

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Vulcanization accelerators and pharmaceuticals.

The parts given in the following examples are parts by weight. They relate to parts of space like kilograms to liters,

The percentages are percentages by weight.

example 1

A vertical high-pressure tube of 500 parts by volume of contents contains a catalyst comprising 10 wt.% Cobalt, 10 wt.% Nickel oxide and 4 wt.% Of copper oxide on alumina filled. After reduction of the catalyst with hydrogen at 250 ⁰ C of the high-pressure pipe each hour 100 parts of ethanol amine are und.350 parts by volume of liquid ammonia were metered at the head, while kept at a temperature of l60 ° C. A pressure of 300 atm is maintained by simultaneously injecting hydrogen. Ammonia is distilled off from the reaction discharge. 115 parts per hour of a mixture are obtained which, according to gas chromatographic analysis, calculated as anhydrous, contains 49 % ethylenediamine, 36% ethanolamine, 6% piperazine and 8% polyamines. The OUT_ yield of ethylenediamine after a single pass is thus based on the reacted ethanolamine.

Example 2

A vertical high-pressure pipe with a volume of 500 parts is with a catalyst containing 10 wt. # Cobalt oxide, 10 wt. $ Nickel oxide, 4% by weight of copper oxide and 0.2% by weight of phosphoric acid, calculated as PoOci on alumina contains filled. Under test conditions, As described in Example 1, II3 parts per hour of a mixture are obtained which, according to gas chromatography Analysis, calculated anhydrous, 44 $ ethylenediamine, 46 $ ethanolamine, Contains $ 3 piperazine and $ 5 polyamines. The yield of ethylenediamine after a single pass is therefore $ 82, based on converted ethanolamine.

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Example J5

A vertical high-pressure tube of 500 parts by volume of contents contains a catalyst comprising 10 wt.% Cobalt, 10 wt.% Nickel oxide and 4 wt.% Of copper oxide on alumina filled. After reduction of the catalyst with hydrogen at 250 ⁰ C of the high-pressure pipe each hour 100 parts of a 80 # by weight aqueous hexanediol be (1.6) solution and 550 parts by volume of liquid ammonia were metered at the head, while kept at a temperature of 22O ⁰ C . A pressure of 300 atm is maintained by simultaneously injecting hydrogen. Ammonia is distilled off from the reaction discharge. This gives 115 parts per hour of a mixture which, according to gas chromatographic analysis, calculated anhydrous, is 49 $ hexamethyleneimine, 23% hexamethylene diamine, 7% 1-aminohexanol- (6), 4% hexanediol- (1,6), 9% N-aminohexyl! Contains hexamethyleneimine and $ 5 polyamines. After the hexamethyleneimine has been separated off, the remainder can be returned to the reactor.

Example 4

A vertical high-pressure tube from 2000 parts by volume of contents with a catalyst comprising 10 wt.% Cobalt, 10 wt.% Of nickel oxide, 4 wt.% Copper oxide and 0.2 wt.% Phosphoric acid, calculated as Pp ^ R ^'au ^ alumina , filled. After reduction of the catalyst with hydrogen at 250 ° C., 500 ml of a 10 ^ solution of 4,4'-bis-hydroxycyclohexylpropane- (2,2) in liquid ammonia are metered into the high-pressure tube every hour from bottom to top, at a temperature of 220 ° C. A pressure of 300 atm is maintained by simultaneously injecting hydrogen. Ammonia is distilled off from the reaction discharge. 53 parts per hour of a mixture are obtained which, according to gas chromatographic analysis, calculated anhydrous, ~ y%> 2-cyclohexyl-2 (4-aminocyclohexyl) propane, 87 $ 4,4'-bis-aminocyclohexylpropane- (2.2), 6% 4,4'-bis-hydroxy-cyclohexylpropane- (2,2) and y $> residue contains. The yield of 4,4'-bis-aminocyclohexylpropane- (2.2) after a single pass is thus 92 $, based on converted 4,4'-bis-hydroxycyclohexylpropane (2.2).

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Example 5

A vertical high-pressure tube of 500 parts by volume of contents contains a catalyst comprising 10 wt.% Cobalt, 10 wt.% Nickel, 2 wt.% Copper oxide and 0.5 wt.% Manganese oxide filled. After the catalyst has been reduced with hydrogen at 250 ° C., 50 parts of diethanolamine and 350 parts by volume of liquid ammonia are metered in every hour at the top of the high-pressure tube, a temperature of 160 ° C. being maintained. A pressure of 300 atmospheres is maintained by simultaneously injecting hydrogen. Ammonia is distilled off from the reaction discharge. 58 parts per hour are obtained of a mixture which, according to gas chromatographic analysis, calculated anhydrous, contains k% ethylenediamine, 22 % piperazine, YJ% N- (β-hydroxyethyl) -ethanolamine, 54 % diethanolamine and 1% polyamines.

Example 6

A vertical high-pressure tube of 500 parts by volume of contents with a catalyst comprising 10 wt.% Cobalt, 10 wt.% Of nickel oxide, 4 wt.% Copper oxide and 0.4 wt.% Phosphoric acid, calculated as PPOC contains filled. After reduction of the catalyst with hydrogen at 250 ⁰ C of the high-pressure pipe and 350 ml of liquid ammonia be at the top of each hour 100 parts of polypropylene glycol (1400 Molgew.ca.) Added to give atur complies of l80 ° C a Tempa?. A pressure of 300 atm is maintained by simultaneously injecting hydrogen. Ammonia is distilled off from the reaction discharge. 102 parts per hour of a product are obtained which, calculated as anhydrous, has an amine number of 76. This corresponds to a degree of implementation of $ 95

-8-209808 / 1957

Claims (4)

- 8 - O.Z. 26 439 Claims 'Process for the preparation of amines from alcohols by reaction with ammonia or amines in the presence of hydrogen and a catalyst containing cobalt, nickel and copper, characterized in that a catalyst is used which, based on the metal content of the catalyst, 70 to 95 percent by weight a mixture of cobalt and nickel and 5 to 30 percent by weight of copper, the weight ratio of cobalt to nickel being 4: 1 to 1: 4. 2. The method according to claim 1, characterized in that a catalyst is used which, in addition to cobalt, nickel and copper, contains up to two of the metals manganese, chromium, zinc, vanadium or silver. 3 «Process according to claim 1 or 2, characterized in that a catalyst is used which, in addition to the metals, contains phosphoric acid or boric acid or their mixture or their oxides or salts. 4. The method according to claim 1, 2 or 3 » characterized in that a catalyst is used which additionally contains an alkali metal or an alkaline earth metal. Aniline & Soda Factory in Baden 209808/1957