DE2844984A1 - METHOD FOR PRODUCING AN AMINE - Google Patents

Description

SHELL INTERNATIONAL RESEARCH MAATSCHAPPIJ B.V. The Hague, Netherlands

Process for the preparation of an amine

claimed priority:

Oct. 17, 1977 - V.St.A. - No. 844093

The invention relates to a method for producing an amine by reacting an alcohol, aldehyde or ketone with up to 25 carbon atoms with ammonia, a primary or secondary Amine in, a reducing atmosphere in the presence of a catalyst.

So far there have been many for the production of amines from alcohols

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Catalysts have been described / e.g. in G & -PS 436 414 typical hydrogenation catalysts / such as copper, for the production of amines from alcohols. In U.S. Patent 3,128,311 Alcohols with ammonia in the presence of a catalyst, aer Nickel, copper and an oxide of chromium, titanium, thorium, zinc or manganese are converted. U.S. Patent No. 3,520,933 is a A number of metals, such as copper and alkali metals, are disclosed which are used in combination with an acid produced by pyrolysis or a polyacid are suitable for the conversion of alcohols to amines.

However, there is no indication in the literature that the specific combination of copper and tin has a synergistic effect on higher selectivity and catalyst stability Has.

The invention therefore relates to a method for producing an amine by reacting an alcohol, aldehyde or ketone with up to 2 5 carbon atoms with ammonia, a primary or secondary amine with 1 to 8 carbon atoms in a reducing atmosphere, which is characterized in that one the reaction is carried out in the presence of a catalyst containing 0.05 to 50 percent by weight of copper, 0.05 to 50 percent by weight Tin and optionally 0.003 to 30 percent by weight alkali metal or alkaline earth metal, each based on the total catalyst, 'Contains on a porous support.

The amount of copper, calculated as percent by weight metal from

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Total catalyst is preferably 0.5 to 20 percent by weight. The amount of tin, also calculated as percent by weight metal of the total catalyst, is preferably 0.5 to 20 percent by weight, and the amount of alkali or alkaline earth metal preferably 0.01 to 10 percent by weight. The catalyst is in the form of oxides and / or metals.

Suitable alkali and alkaline earth metals for the catalyst are the metals in groups IA and HA of the periodic table, which are in the form of their salts, e.g. as lithium, sodium, Potassium, rubidium, cesium, magnesium, calcium, strontium and barium salts. Sodium salts are preferred.

The carrier material for the catalyst used in the process according to the invention are conventional porous, heat-resistant carrier materials which are resistant both to the starting material and to the products formed in the process according to the invention. The carriers can be of natural origin or synthetic. Very suitable are silicic acid and / or aluminum oxide containing substances to aluminum oxides, charcoal, pumice stone, magnesium oxide, zirconium oxide, diatomaceous earth, fuller's earth, silicon carbide, porous agglomerates of silicic acid and / or silicon carbide, clays, artificial and natural zeolites and ceramic products. Heat-resistant products which contain silica and / or aluminum oxide, in particular ^ -aluminum oxide entnaiteride materials, are particularly suitable.

The catalyst used in the process according to the invention

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A carrier can be made in a number of ways, for example by precipitating the metal components together a carrier in powder form or in spheres or by co-precipitation with the carrier from aqueous solution e.g. sodium carbonate, or hydroxide. Preferably wira aer The catalyst is produced by using a support material impregnated with an aqueous solution of suitable salts of active metals, then dries and the impregnated Carrier caicinated at temperatures from 100 to 600 C. The preferred solvent is water, but some can be used use organic solvents. Suitable salts for aqueous systems are chlorides, bromides, nitrates / acetates and lactates. Alkali metal tin (II) salts and tin (IV) salts are special suitable because they provide both tin and the alkali metal. On the other hand, you can also find solutions from Spray-dry salts of the active metal and the carrier and calcine at temperatures of 100 to 600.degree.

Before use, the one used in the process according to the invention is used Catalyst activated by heating in a reducing atmosphere, e.g. in hydrogen or ammonia. Preferred is hydrogen. A suitable temperature for this activation is between 250 and 600 C. The time required for this depends on the temperature, i.e. the higher the temperature, the shorter the time. This activation usually takes 6 minutes up to 24 hours, although times outside these limits are also suitable. For economic reasons jeaocn one will be within the specified limits remain.

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The starting material for the process according to the invention is aliphatic, cycloaliphatic / arylaliphatic alcohols, Ketones or aldehydes with up to 25, preferably up to 20 carbon atoms, are preferred. These compounds can also be unsaturated be, e.g. with 1 or 2 olefinic double bonds, and carry substituents under the given reaction conditions are inert, e.g. alkyl radicals with 1 to 4 carbon atoms that are bonded via ether bridges. Of particular economic Significance are aliphatic or cycloaliphatic alcohols / aldehydes with up to 20 carbon atoms, e.g. ethanol / al, propanol / al, isopropanol, butanol / al, isobutanol / al, 2-ethylhexanol / al, Decanol / al, dodecanol / al, hexaaecanol / al, cyclopentanol, Cyclohexanol, cyclooctanol, cyclododecanol, benzyl alcohol / aldehyde, phenylethyl alcohol / aldehyde, 1,4-butanediol / al, 1,6-hexanediol / al, 1,5-pentadiol / al and 1,8-octanaiol / al.

Examples of suitable ketones are acetone, methyl ethyl ketone, Methyl isobutyl ketone, phenyl methyl ketone, phenyl ethyl ketone, 3-decanone, 5-dodecanone, cyclopentanone, cyclohexanone, cyclooctanone and cyclododecanone.

Preferred amines for the process according to the invention are primary or secondary amines, e.g. alkylamines, cycloalkylamines or arylalkylamines with 1 to 8 carbon atoms, in particular Alkyl amines with 1 to 4 carbon atoms and one amino group in the molecule. Specific examples of suitable juuine are monomethylamine, Dimethylamine, methylethylamine, and monoethylamine Diethylamine. Monomethylamine and dimethylamine are preferred.

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In the process according to the invention, the alcohols, aldehydes or ketones are expediently used with at least one equivalent Ammonia or amine reacted, the ammonia or the amine can also be used in excess, e.g. up to 50, preferably up to 20 moles of ammonia or / or ammonia to be converted Hydroxyl or carbonyl group.

The reaction is conveniently carried out at a temperature of 160 to 350 C, preferably from 180 to 300 C, and a reaction pressure from 1 to 275 bar, preferably 10 to 70 bar, carried out. The reaction is preferably carried out in the presence of Hydrogen through, conveniently at hydrogen partial pressures from 1 to 200 bar, preferably 5 to 70 bar. It is beneficial to have a molar ratio of hydrogen to alcohol, Aldehyde or ketone above 1 to use. The reaction system can also partially with inert gases, such as nitrogen or Argon.

The process according to the invention can be continuous or discontinuous be performed. In the case of a discontinuous procedure, e.g. a high-pressure autoclave, which is operated with is equipped with a stirrer with the alcohol, aldehyde or ketone, the amine or ammonia and the catalyst charged, charged with hydrogen and heated to the reaction temperature. After the mixture has reacted for the desired time, the autoclave is cooled, the excess hydrogen is blown off, the products are worked up in a conventional manner.

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In the case of a continuous procedure, e.g. a vertical high pressure column with the catalyst, alcohol and aem Amine charged at the top of the column. At the same time there is hydrogen fed into aie column in cocurrent or countercurrent. Of the Hydrogen is conveniently fed back into the cycle in a process. The times of the reaction are appropriate Maintain temperature and pressure conditions. The trouu-kt is taken from the lower Enae aer column, freed from hydrogen peat una processed in the conventional way.

An anaer, continuous way of working is best aarin, aass one

aer
the reaction mixture) is dispersed in the / catalyst over

Lets trickle filler or damming body in a tower.

The examples illustrate the invention.

example 1

A solution of 16 g of copper nitrate, of the formula Cu ('AO, ).,. 3h..0 and 15 ml of water are used to impregnate Ab g aluminum

2
oxide (18 30 mesh, surface area 263 m / g, pore volume 0.2 ml / g). The impregnation takes place with thorough mixing in order to ensure an even distribution of the metal salts on the aluminum oxide.

The impregnated aluminum oxide is poured into a vertical pipe. Air at a speed of 400 uvl / minute weu

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passed over the catalyst, the temperature gradually increasing at intervals of 30 minutes to the following values v / iru: 80, 100, 125, 150, 175, 200, 250, 300, 400 and 500 ° C. The calcined catalyst is cooled to room temperature impregnated with 3 g of sodium stannate (IV) in 1b ml of water. the The calcination is repeated, the catalyst is then added in stages from 125 to 500 ° C. in the course of 2 hours with nitrogen diluted viassstoff reduced.

Example 2

45 g of alumina (Reynolds RA-1, 1 χ ä 30 mesh, surface

about 260 m / g, pore volume about 0.26 ml / g) are with a Impregnated solution of 16 g of copper nitrate in 16 ml of water calcined as in Example 1. The catalyst is then treated with a solution of tin (II) tartrate in 1 nl of water and 1 ml Nitric acid impregnated again and calcined and reduced as in Example 1.

10 ml of this catalyst are placed in a reactor with a trickle phase filled in, dimethylamine and laurylaluehyde (l-doaecanal) become at an hourly liquid-space velocity of 1.1 and a molar ratio of amine to alumina of 3: 1 fed in. The temperature of the reactor is set to 10 ° C held. Hydrogen is fed into the reactor at a rate of 100 ml / minute. The pressure v / iru auC 26 bar held. After 1 hour a molar aldehyde conversion is obtained of 98.9% and a molar selectivity to üiraethyl-

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dadecylamine of 77.3%. After 2 hours the conversion is 100% and the selectivity 70%.

Example 3

48 g of aluminum oxide (Reynolds RA-1, 18 χ 30 mesh) are included impregnated with a solution, aie by heating 4.6 g of copper nitrate with 20 ml of aqueous ammonia and adding 1 g of i'jatriuiustannat (IV) is made. The catalyst is calcined and reduced according to Example 1 and contains 2.4 percent by weight Copper, 0.71 percent by weight tin and 0.7 percent by weight Sodium.

10 ml of this catalyst are introduced into a reactor with a trickle phase and a volume of 25 ml, dimethylamine unu Dodecanol have a liquid hourly space velocity of 1/1 and a molar ratio of amine to alcohol of 3: 1. The temperature of the reactor is wiru kept at about 250 C. Hydrogen at a rate of 100 ml / minute is fed into the reactor under pressure is kept at 26 bar. After 2 hours 30 minutes the molar alcohol conversion is 95.4%, the molar selectivity to Dimethyldodecylamine 78%.

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Example4

2 g of copper nitrate are dissolved in 15 ml of aqueous ammonia _f mixed with 0.5 g of L sodium stannate (IV) and used to impregnate 30 g of aluminum oxide (Reynolds RA-1). The catalyst is then calcined according to Example 1 and reduced and contains 4 percent by weight copper, 1.2 percent by weight tin and 0.87 percent by weight sodium.

10 ml of this catalyst were introduced into a reactor with a trickle phase and a volume of 25 ml, dimethylamine and the like 1-Dodecanol have a liquid hourly space velocity of 1.1 and a molar ratio of amine to alcohol of 1.4: 1 fed into the reactor. The reactor wirci kept at a temperature of 244 ° C. Hydrogen at a rate of 100 ml / minute is fed into the reactor, the pressure is kept at 26 bar ". After 90 minutes the molar alcohol conversion is 60.3%, aie molar selectivity to dimethyldodecylamine 94%.

The temperature of the reactor is then increased to 25O ° C / after A conversion of 79.1% and a selectivity to dimethyldodecylamine of 09.4% are obtained for 90 minutes. After 2 hours 30 Minutes, the alcohol conversion is 82% and the selectivity to dimethyldodecylamine is 88.9%.

This process is repeated with the same catalyst as however, Dimethylamine, Triinethylarnin and 1-Douecanol are used in fed in a molar ratio of 3: 2.3: 1. After 2 hours and 30 minutes a conversion of 89.7% and one

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Selectivity to dimethyldoecylamine of 05.7%.

Example 5

24 g of aluminum oxia (Reynolds RA-1, 18 χ 30 mesh) are mixed with 1.5 g of sodium tannate (IV) are added to 10 ml of water, then calcined according to Example 1 and reduced. The catalyst contains 2.9 percent by weight tin and 0.9 percent by weight sodium.

10 ml of this. Catalysts were introduced into a reactor with a trickle phase and a volume of 25 ml, dimethylamine and 1-dodecanol were fed in with an hourly liquid roughness rate of 1.1 and a molar ratio of amine to alcohol of 3: 1. Hydrogen is fed into the reactor at a rate of 100 ml / minute, the pressure is kept at 26 bar. At a reactor temperature of 257 ° C, there is no alcohol coating. At 300 ⁰ C is obtained after 1 hour of operation a molar Alkoholumwanalung of 9% with an approximately yleichen distribution between Methylaouecylamin una Dimethyldoaecylamin.

Example 6

According to aer: the procedure of Example 1 becomes a catalyst made containing 7.6 percent by weight copper, 2.7 percent by weight tin and 0.9 percent by weight sodium.

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Vl -

ήψ

25 ml of this catalyst were placed in a reactor with a trickle phase and a volume of 25 ml, Dime thy laiain una 1-Dodecanol are filled with an hourly liquid space velocity of 0.6 and a molar ratio of Mn to alcohol of 3: 1. Hydrogen is going at a rate fed in from 180 ml / minute, eier pressure is on 2ü bar held. The results are summarized in Table I.

Table I.

Experimental
üauer,
Stunts reactor
temperature,
° C Alcohol-
walling,
Mole percent Selectivity too
Dimethyluouecyi-
amine, mole percent 15.3 21 * 30.3 100 17.8 239 38.6 97.5 23.4 247 97.4 96.9 42.4 24d 93.7 96.6

Example 7

According to the procedure of Example 1, a catalyst is prepared, which contains 8.3 percent by weight copper, 2.3 percent by weight tin and 1 percent by weight sodium.

10 ml of this catalyst were poured into a reactor with a trickle phase and a volume of 25 ml, dimethylamine unu n-Butanol are produced at an hourly liquid space velocity

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speed of 1.1 and a molar ratio of amine to alcohol fed in at a rate of 3: 1. Hydrogen is fed in at a rate of 100 ml / minute, the pressure is increased to 26 bar held. At a reactor temperature of 250 ° C., an alcohol conversion of 68.8 mol percent is obtained after 1 hour Selectivity to dimethylbutylamine of about 100 mole percent. At 273 ° C., a conversion of 93.4 mol percent is obtained after 1 hour and a selectivity above 9 9 mole percent.

Example Ö

25 g of aluminum oxide (Reynolds RA-1, 18 χ 30 mesh) are added first with 8 g of copper nitrate in 4 ml of water, then with 1.1 g of tin (II) tartrate impregnated in 3 ml of water and 1 ml of nitric acid, then calcined according to Example 1 and reduced. The catalyst contains 5.4 percent by weight copper, 1.5 percent by weight tin and 0.5 percent by weight sodium (catalyst A).

Catalyst B is prepared accordingly, but with slightly different metal concentrations; it contains 9.3 percent by weight Copper, 1.6 percent by weight tin and 0.3 percent by weight sodium.

10 ml each of these catalysts are introduced into a reactor with a trickle phase and a volume of 25 ml. Monomethylamine and 1-dodecanol in a molar ratio of i: 1 unu a liquid hourly space velocity of 1.1

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are fed in. Hydrogen is moving at one speed fed in at 100 ml / minute, the pressure is kept at 26 bar. The results are summarized in Table II.

Table II

Alcohol selectivity, mole percent

Catalyst Tempe- Trial-

rature, duration, transformation, methyl- C + C, -

o_ hours MoL- uouecyl-C - percent amine ^ ¹ "

A 220 1.5 72.6 77.6 20.5

240 1.5 83 j 2 67.3 30.1

250 1 90 61.3 35.4

B 210 1.5 32.6 47.6 52.4

225 1.5 38.8 37.3 62.7

'280 1.75 3Oj2 31.7 64.9

295 1.5 9OjI 31j0 64.8

Example 9

According to the procedure ues example 1, the in table III specified catalysts produced. The carrier is alumina.

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Table III

catalyst Copper,
Weight
percent Tin,
Weight
Drowning Sodium,
Weight
per cent A. 1.4 0.96 B. 3/0 1.4 C. V 3; 1 ¹ IS D. 2.0 2.9 ¹ JS E. 0.44 0.55 ¥ 3/7 1.0 0.29 G ² f3 0.23 0.51

Each catalyst is filled into a reactor with a trickle phase, Methylamine and 1-douecanol in a molar ratio of 3: 1 and an hourly liquid space velocity of 1.1 are fed in. Hydrogen is going at a rate fed in at a rate of 100 ml / minute, press on 26 bar held. The results are summarized in Table IV.

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Table IV

Alcohol selectivity, .'- iolprozenc

Catalyst Tempe- Trial-

rature, duration, wall, i-Iethyi- C-,. -> C., - o Stunaen Mol- aouccyl- j ^{1 Aj}

orczenc air.in ""

A 225 1.5 25.3 71.4 23.8

250 3 50.7 x 51.4 46.9

B 245 1+ 14.3 92 8

280 2 76.3 51.1 48 ^

C 215 Ij5 4 100

253 l _r 5 5.3 100

277 1 30 69.4 30.6

303 1 ■ 70.3 43.6 56.4

D 230 2 27.5 82.2 4.4

E 210 2.5. 41 94.8 3.0

235 l 73.9 89.1 9.3

250 1.75 92.5 80.2 17.7

P. 223 2 9.4 79.6 8.2

250 2 17.2 81.3 10.3

G 222 2.5 13.5 90 4

Example 10

1.1 g of tin (II) tartrate are dissolved in 1 ml of water and 1 ml of nitric acid dissolved and mixed with a solution of 16g copper nitrate in ml water. 45 g aluminum oxide (Reynolds ItA-1) are impregnated with this solution, then according to Example 1

calcined. The catalyst contains 7.1% by weight copper,

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0.94 percent by weight tin and 0.4 percent by weight sodium and is introduced into a reactor with a trickle phase. Ammonia and 1-Dodecanol are in a molar ratio of 3.5: 1 and a liquid hourly space velocity of 1.1 in the Fed into the reactor. Hydrogen is fed in at a rate of 100 ml / minute, the pressure is kept at 26 bar. The results are summarized in Table V.

Table V

Reactor alcohol selectivity, mol percentage

tempe- experimental u: r- '_

rature, duration, var.uluny, didodecyl- 'iridouecyl-

o Hours of MoL amine * amine

hours Mon L- CZCUt 208 · 2 73.8 .232 2 83 _; 4th

31.1 6 * 1.2 Example 11

The procedure of Example 10 is repeated with a catalyst containing 7.6 percent by weight copper, 3.1 percent by weight tin and 1.6 percent by weight sodium. ammonia and 1-dodecanol are fed in a molar ratio of 1.5: 2. The results are summarized in Table VI.

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Table VI

Reactor Alcohol Selective! Tat, mole percent

tempe- trial- um-

rature, duration, wanalung, _didodecy i_ Tridoäecyl-

o Stunaen «oil _{am ± n amin}

________ percent

313 $ 2 52.6 ■ 91

317 3.7 77.2 io, 8 89.2

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Claims (7)

Claims 1. A method for producing an amine by reacting a Alcohols, aldehydes or ketones with up to 2 5 carbon atoms with ammonia, a primary or secondary amine with 1 to S carbon atoms in a reducing atmosphere, characterized in that the reaction is carried out in the presence of a catalyst which is U / 05 up to 50 percent by weight copper, O / O5 to 50 percent by weight Tin and optionally 0.003 to 30 percent by weight alkali metal or alkaline earth metal, each based on the total catalyst, contains on a porous support. 2. The method according to claim 1, characterized in that aluminum oxide is used as the carrier. 3. The method according to claim 1 and 2, characterized in that a catalyst is used which is 0.05 to 20 percent by weight Copper and 0.5 to 20 percent by weight tin, each based on the total catalyst. 4. The method according to claim 1 to 3, characterized in that one uses a catalyst which is also 0.01 to 10 percent by weight Contains alkali metal or alkaline earth metal. 5. The method according to claim 1 to 4, characterized in that hydrogen is used as the reducing atmosphere. 909816/1020 6. Method.nach Claim 1 to 5, characterized in that uass the reaction is carried out at a pressure of 1 to 275 bar. 7. Process according to Claims 1 to 6, characterized in that the reaction is carried out at a temperature of 160 to 350.degree. 909816/1020