DE1941290A1 - Process for the production of saturated aliphatic, secondary amines - Google Patents

Description

FARB ^ iSRZE HOSCEST AG., Formerly Meistöfiiucius & Brüning Gendorf plant

1496 reference number: P ,. "Gd .......

Eatum: ..?. \
Dr.Br/Mü

" Process for:? Production of saturated, aliphatic ^ secondary Asiine"

The invention is a. Method of manufacture saturated, aliphatic secondary amines by hydrogenation of unsaturated or partially unsaturated nitriles or nitrile mixtures with 8-22 carbon atoms, if appropriate in mixture with unsaturated or saturated amines named chain length with simultaneous elimination of ammonia ' in the presence of fixed-bed hydrogenation catalysts, which is characterized in that in a first reaction stage, the products mentioned at hydrogen pressures of 100-300 atü and 100 - 200 ° C continuously to form a mixture hydrogenated primary, secondary and tertiary saturated amines and this mixture in a second reaction stage at 0 50 atü and temperatures of 120-220 ° C in the presence of hydrogenation catalysts, optionally with the addition of Hydrogen, continuously deaminated.

From German patent specification 1 230 243 it is known that one saturated and unsaturated nitriles by continuous hydrogenation in the presence of a copper-chromium fixed bed contact on silica gel with high yield in the · corresponding secondary Can convert amines. An attack on the carbon-carbon double bond in the case of unsaturated nitriles

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not taking place. Uni too, for example, to distearylamine produce, one has to rely on stearyl nitrile as a starting base. For economic reasons, however, it would be desirable to start from the cheaper tallow fat nitrile and when the olefinic double bond is removed at the same time, the corresponding saturated secondary amines are obtained to be able to. However, two different reactions are required for this:

1. Hydrogenation of the olefinic double bond in addition to the hydrogenation of the nitrile group, for which high pressures are necessary , ■ "■■ .. '■:

2. Formation of secondary amines with elimination of ammonia, this preferably requires low pressures.

It is difficult to combine these two conditions with one another in one reaction stage if value is placed on high space-time yields with, at the same time, high yields of saturated secondary amines. At low pressures, at which secondary formation and deamination proceed with a high space-time yield, the olefinic double bond remains unaffected. At high pressures, on the other hand, although the olefinic double bond is erected, deamination to the secondary amine is by no means sufficient. In addition, for the highest possible yield of secondary amine, it is necessary to remove the ammonia formed from the reaction equilibrium. In the known discontinuous production processes, which are based on the fact that both longer-chain aliphatic nitriles with 8-22 carbon atoms and the corresponding amines or nitrile-amine mixtures of catalytic hydrogenation at 7-70 atm and 110-220 ° C. are removed you get the ammonia by two different methods. According to one method, which is described in German Patent 963,518, to remove the ammonia, the mixture of the same with hydrogen is depressurized to atmospheric pressure and hydrogen is injected again to continue the hydrogenation or the formation of Seloindärbildung. This process is repeated so often, _ ₀ ^ 109811/2189; _{BW3 0RK31NAL}

until the gavüiisclrte secondary salary of at least SO $ . is reached. According to example 2 of this patent specification, the amnonium is removed at least six times and the quay is then rehydrated again at 20 ° C. and 14 atmospheres with new hydrogen each time. Similarly Meise, the procedure according to British Patent Specification 759,291, in which at high ICatalysatoraufwand only Raux-Zsit-Ausbcuten ve :: 50 g / l Xoircakt / h reaches v / ground. According to US Pat. No. 2,734-232, autoclaves are discontinuously based on the principle of intermittent relaxation and pressure hydrogenation. .

Another principle consists in the fact that the mixture of A ^^ ionialc and hydrogen can be continuously withdrawn from the hydrio-r-ösfaß, which is under pressure, - the aim is to be washed out and ac: i oötröcacieten hydrogen to be brought back (French. Pat ent-L; chrif "c 1 173 S52 ;.

Al _o "csehen. Davcn, da2 it in the above methods

uiad the Kcr.taktTsrrauch z: it 0.4 - 5 $> (be ^ o ^ sn on Aus ~ ar _ic r £ - produlct) sJ. '. s is high, the main disadvantage is that AiZjionialc from de ^ i I-leaction-equal ^ evicht after very time-consuming, expensive and sometimes quite complicated procedures. be removed a.u5. At the same time, the hydrogen, which is indispensable for the hydrogenation process, is lost. -

It has now been found that nano aliphatic, saturated secondary amines and their mixtures with a high Reua-Sit yield from unsaturated lutilites or from saturated-unsaturated nitrile mixtures containing 8-22 carbon atoms, "cz \ -r. From the nitriles mentioned can be obtained in a mixture with unsaturated and saturated amines of the required carbon chain with simultaneous elimination of ammonia in the presence of fixed-bed hydrogenation catalysts if the reaction is carried out in two stages by adding the unsaturated nitriles optionally susainmen- nit to the products just mentioned in the first stage a mixture of primary, secondary and

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hydrogenated tertiary saturated amines and this vi ^ aisch in a second stage in the presence of hydrogenation catalysts, with ^ ede stage among those for the respective Reaction proceeds optimally.

The two-stage process according to the invention is carried out in hygienic apparatus in which the catalysts are firmly enngcioaux smc. In a first rLScwCcn-onssJune Q'fi ~ cs'CQiVz a-uS preliminary product a Gc-uis.ch. from saturated. Aninen, for example 40 - 50 fo each from prira. and sec. and consists of 2 - 7 £ of 3 tertiary amines. In the 2nd reaction stage, arsaoniaka ο cleavage causes the Sei: undär content to rise to ζ .3. 90 i *> and the result is the saturated secondary anines according to the invention. While the hydrogen is circulated in the first stage, hydrogen is not absolutely necessary in the Ξλ / ειΐβη stage. .

The two reaction steps -konnen ENTV ^ eder getremre yeneinander performed or combined to form a complete Itcntinuus ver cen. Here the aminmoniac, which forms in the first stage, goes together with the amingeal from this stage into the second stage, so it does not need - how. in the initially discontinuous process - to be removed during the reaction. Besides this important advantage, another is that it is contrary to the Brit.Patent 759 2S1 before hydrogenation not necessary Etwal h to about TOO to erhitzen- ,, among other things, the moisture to remove the presence of the catalysts in Einsatüprcdukte ⁰ C. In the present invention, the starting products can contain up to 5 5 »water without the course of the reaction being disturbed.

As starting materials for the present process Accessible secondary amines can be unsaturated fatty acid nitriles serve as they are made from unsaturated fatty acids such as undecylenic acid, oleic acid, erucic acid, be won. Mixtures of unsaturated compounds are particularly suitable and saturated nitriles, which are derived from higher fatty acids

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Fats and oils are produced, such as tallow fatty acid,. Coconut fatty acid, palm kernel lactic acid, cottonseed oil fatty acid, Tall oil fatty acid and trans fatty acid. If necessary, synthetic mixtures of saturated and unsaturated can also be used Nitriles together with saturated and unsaturated amines get used.

Practically all hydrogenation catalysts can be used as catalysts for the first reaction stage. Cobalt and nickel contacts on kieselguhr are preferred. They preferably contain 45 pounds of cobalt or 55 f ° nickel. "For the second reaction stage - deamination - in addition to cobalt contacts, mainly copper-cadmium or copper-chromium contacts, preferably an abrasion-resistant Küpfer-chromium-potassium contact German Patent 1,280,243, the $ 20-30 copper, $ 0.5-3 chromium and $ 0.5-2 potassium

on a wide-pored silica gel with a specific top

contains an area of 250-350 m ~ g as a carrier. The contact consumption in the first stage is approx. 0.03 7 ° cobalt or 0.03 "f ° nickel and in the second stage 0.015 fo cobalt and 0.007 fo copper.

The process according to the invention operates with a high space-time yield. It is generally 500-1500 g of amine per liter contact volume / hour. Temperatures and pressures during the reaction are variable within wide limits. In the first Step one works at 100 - 300 atü and 100 - 200 ° C and in the second stage at 0 - 50 atmospheres and 120 - 220 ° C.

If the reaction is carried out optimally, in addition to the high throughput, yields of secondary amines of up to 90 % are achieved. The secondary fatty amines produced in this way are light in color and practically water-clear. They are used as starting materials for the production of textile auxiliaries, disinfectants, antistatic agents and organophilic ammonium bentonites.

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' Example 1:

1300 g of oleyl nitrile (iodine number 90) per hour are continuously passed into a hydrogenation furnace over 2000 ml of a permanently installed cobalt contact ^{containing 45 c} ß> cobalt on kieselguhr at 200 atm. Hydrogen pressure and 160-165 ° C. This gives an amine mixture which consists of 40 % primary, 57.5% secondary and 2.5% tertiary amine and has an iodine number of 2. The contact consumption is 0.02 fo cobalt. This amine mixture is continuously in a second hydrogenation furnace at 200 ° C and. 10 atm while simultaneously passing of 12 1 of hydrogen per hour over 2000 ial a copper contact conducted, containing 25 copper fo '^ 0.6 chromium and 1.1 $> potassium on silica gel. After the reaction has ended, an amine mixture is present which contains 90.3 ° secondary amine, 5.9 ° primary amine, and 3.8 ° tertiary amine with an iodine number of 2. The ".. contact consumption is 0.07 f ° copper. ■

Example2:. . ■

Tranfettsäurenitrii with an iodine number of 100 is allowed to trickle with a load of 1000 g per liter of contact space per hour over 2000 ml of a cobalt contact as in Example 1 at 180 ° C. and 200 atmospheres and an amine mixture of 67 ° secondary amine is obtained , 25.5 ° i $ 7.5 primary amine and tertiary amine having an iodine value 2. The contact consumption is 0.031 $ cobalt.

The amine mixture obtained in this way is passed continuously over 2000 ml of a copper contact as in Example 1 in a second hydrogenation apparatus at 200 ° C. and 25 atm. An amine mixture is obtained consisting of 86% secondary amine, 5 ° primary amine and 9% tertiary amine with an iodine number of 2. The contact consumption is $ 0.007 copper.

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Tallow fatty acid nitrile with a Jo dz ahl. from 53 v / earth with a load of 1500 g per liter of contact space per hour over 18,000 ml of a nickel contact with 55 Y ° nickel on diatomaceous earth at temperatures of 170 ° C and 100 atm hydrogen pressure continuously passed, with an amine mixture .resultiert , which contains 58 Jo secondary, 50, 5 i ^a primary and 5.5 $ tertiary amine with an iodine concentration of 2. The contact consumption is 0.029 ^c / o nickel. "". .

This amine mixture is in a second hydrogenation apparatus over 18,000 ml of a cobalt contact containing 45 l = cobalt. Contains diatomaceous earth, allowed to trickle continuously at -190 ° C and 15 atmospheric pressure. An amine mixture is obtained from SO, 5 $ secondary, 9.5 £ primary and 10 % tertiary amine with a Jcdüahl of 1.5 · The contact consumption is 0.015 $ cobalt «

Example 4i

75 / * coconut fiber acids! Tr il with an iodine steel vcn 14 Vverden, together with 25 ? ° dioleylamine der Iodine steel 80 with a load of 1000 g per liter of contact space per hour over 10,000 ml of a cobalt contact as in Example 1 at 160 ° C and 300 atm continuously. The amine mixture obtained from setst 56.0% secondary, 41.5 * f ° primary and tertiary amine 2,5 ί ° an iodine value of 0.4 together. The contact consumption is 0.021 <fo cobalt.

This mixture is left in a second apparatus over 10,000 ml of a copper-cadmium contact, which contains approx. 25 # copper and 5 % cadmium on silica gel, at 210 ° C. and 0 atmospheric pressure while at the same time 40 l of hydrogen are passed through trickle continuously every hour. An amine mixture of 85.0 ^; '# secondary, 10.5 # primary and 4.5% tertiary amine with an iodine number of 0.4 obtained. The contact consumption is 0.007 fo copper.

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example 51

A mixture of 40% oleyl nitrile, 20% dodecyl nitrile, and 40 <? O tallow fatty amine with a total iodine number of 52 with a load of 1200 g / l Eontaktraum / h more than 10 000 ml of a nickel contact as in Example 3 at 20p atm hydrogen pressure and 180 ° C passed continuously. The amine mixture is primary the iodine value of 3, and consists of 55 fo, secondary 40% and 5 $ tertiary amines. The contact consumption is .0.018 % nickel.

This mixture is allowed to flow continuously through a reducing valve flow into a second reaction furnace containing 10,000 ml of an Eupfer-chromium contact as in Example 1.

The deamination takes place at 10 atm and 180 ° C with the addition of hydrogen. The result is an amine mixture of 88 fo .

secondary, 5 ^ primary and 7 ° tertiary amine.

The contact consumption is 0.05 % copper.

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Claims (6)

Claims 1.) Process for the production of saturated, aliphatic », secondary amines by hydrogenation of unsaturated or partially unsaturated nitriles or nitrile mixtures with 8-22 carbon atoms, optionally mixed with unsaturated or saturated amines. the chain length mentioned 'with simultaneous elimination of ammonia in the presence of fixed bed hydrogenation catalysts, which is characterized in that one. the said products ■ hydrogenated in a first reaction stage continuously primary at hydrogen pressures of 100 -300 atü.und 100.- 200 ⁰ C to a mixture of secondary and tertiary amines and saturated atm, this mixture in a second reaction stage at 0-50 and. Temperatures of 120 - 22O ⁰ C in the presence of hydrogenation catalyst s, deaminated optionally with the addition of ¥ on Hydrogen continuously. 2.) Method according to Claim.1, characterized in that, that the two reaction stages are in direct succession are switched and carried out fully / continuously. -. -. 3.) Method according to claim 1 and 2, characterized in that that in the first stage nickel or cobalt catalysts begins. 4.) Process according to claim 3, characterized in that catalysts are used which contain 45 % cobalt or 55% nickel on kieselguhr. 5.) Process according to claim 1 and 2, characterized in that catalysis * containing copper is used in the second reaction stage. 109311/2189 - ίο - 6.) The method according to claim 5, characterized in that that copper-chroa-xalium or '·. Copper-cadmium catalysts Find use. BAD ORiGINAL 109811/2189