DE2114170A1 - Direct synthesis of aromatic diamines - Google Patents

Description

E. I. DU PONT. DE NEMOURS AND COMPANY lOth and Market Streets, Wilmington, Delaware I9898, V.St.A.

Direct synthesis of aromatic diamines

Until now, aromatic diamines, such as the phenylenediamines, have been obtained by reducing the corresponding dinitro or nitroamine compound synthesized. Metaphenylenediamine, for example, is obtained by reducing m-dinitrobenzene. Ortho- and para-phenylenediamine is obtained by reducing o-nitroaniline or p-nitroaniline.

The methods described above are costly and therefore more straightforward synthetic methods are particularly desirable Systems that can be well adapted to large-scale commercial production.

It has now been found that a straightforward process for making aromatic diamines can thereby be realized may that a monoamino-substituted, aromatic

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Compound in the presence of a nickel / nickel oxide catalyst composition at a temperature in the range from 150 ° C to 500 ° C and at a pressure in the range of 10 to 1000 atmospheres reacted with ammonia and the resulting aromatic diamine is isolated.

The Niekel / nickel oxide catalyst system can be used alone or in Combination with a compound such as a carbonate or oxide of another metal, especially an oxide that a cubic crystal structure, such as zirconium or strontium oxide, can be used. To other oxides and carbonates of this kind, which can be used together with nickel oxide, include those of barium, calcium, Magnesium, zinc, iron, titanium, silicon, aluminum, thorium, uranium, cerium or one of the alkali metals. These can be used together with the nickel / nickel oxide compound or in conjunction with zirconium oxide or strontium oxide. Combinations with certain clays, such as diatomaceous earth, can also be used. The compounds mentioned can in the manner of a ^ carrier or as a promoter for the nickel / nickel oxide system works.

Among the mentioned compounds that can be used together with the nickel / nickel oxide catalyst are those of strontium, barium, calcium and the alkali metals are believed to be predominant in the catalyst mass present as carbonates. In view of the hydrolytic conditions that prevail in the catalyst preparation, In some cases, the carbonates can be hydrolyzed to the corresponding oxides or hydrous oxides. the Compounds of the other metals mentioned, that is,

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bonds of zircon, magnesium, zinc, iron, titanium, aluminum, silicon, cerium, thorium and uranium are, as is believed to be present in the catalyst mass as the oxide or hydrous oxide.

As indicated, the catalyst composition for the direct, one-step production of the aromatic diamines is a combination of metallic nickel}, with a nickel oxide. Possibly can be the oxide or carbonate of at least one other metal, such as zirconium or strontium, the Combination can be incorporated. These catalyst combinations can generally be prepared in that the nickel oxide is reduced in a hydrogen atmosphere and then oxidized or conditioned by the obtained Mass is exposed to an oxidizing atmosphere prior to its use in the amination. This is achieved by that assumed a solution of the soluble nickel compound or a solution of the soluble nickel salt with the soluble compound of another metal, such as zirconium or strontium, is mixed and then the material with a base such as sodium hydroxide, lithium hydroxide, potassium hydroxide, sodium bicarbonate, potassium carbonate, ammonium carbonate or sodium carbonate, is precipitated. The precipitated material that is in the form of the carbonate or oxide or preferably of the hydrous carbonate or oxide is present, is filtered, washed, air-dried and at least partially reduced with hydrogen, finally cooled to room temperature and a suitable amount of air or exposed to oxygen or possibly water. The solid product obtained is then ready for use direct amination attempts.

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Suitable Niekel / nickel oxide catalyst compositions can also are produced by * that elemental nickel is incorporated into the nickel oxide by electrolytic reduction or by decomposition of a nickel compound such as nickel formate or nickel carbonyl.

The reaction conditions under which the invention Processes that can be carried out depend on the particular reactants and catalyst masses that are used should be. In general, temperatures in the range of about 150 ° C up to about 500 ° C can be used. The implementation can be performed on bridges ranging from about 10 atmospheres to about 1000 atmospheres.

The inventive method can either in; discontinuous or be carried out in continuous operation. For discontinuous operation, the Apparatus e.g. a moving autoclave or a pressure tube, whereby the reactants are introduced, the reactor closed and after a predetermined period of time at elevated temperature the apparatus and the contents be cooled to room temperature, relieved excess pressure by opening and the desired reaction product, which the contains aminated, aromatic compound, of unreacted, aromatic compound and by-products conventional methods such as distillation, crystallization and so on.

PUr can operate in a continuous manner Process for example in plague bed reactors, packed vessels or snakes, with ammonia and the aromatic

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Compound continuously introduced into the reactor and passed through a bed containing the catalyst mass or carried out in a moving bed, with the reaction bed and the other reactants either running in the same direction or in a countercurrent to one another will. Yet another type of continuous operation is one. Fluid bed or .sole insulation type, with which the catalyst mass is fed into the reactor as a slurry in one or more of the reactants.

In each of the two types of reactor, namely in the discontinuous one driven and continuously driven, the aromatic compound and the ammonia can through separate devices can be introduced, or they can be mixed and used as a single device prior to entering the reactor Electricity can be supplied. The nickel / nickel oxide mass can be regenerated periodically, or oxygen can be used or an oxygen-containing gas such as air, especially in a continuous system, into the reaction bed continuously be introduced to keep its catalytic activity at the desired level.

Among the aromatic compounds that are used as starting materials for The preparation of aromatic diamines to be used include monoamino substituted, monocyclic, aromatic Hydrocarbons, such as aniline, monoamine-substituted, polycyclic, aromatic hydrocarbons such as those of Bi phenyl, naphthalene, anthracene or phenanthrene, and other monoamino-substituted aromatic compounds, such as those derived from pyridine, quinoline, diphenyl ether or benzonitrile, as well as aromatic hydrocarbons, those substituted by alkyl groups and amino groups

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are, e.g. such compounds as toluidines, the xyIidines, mono- and polyalkylated naphthylamine and the corresponding Biphenyl, anthracene and phenanthrene compounds. If desired, the aromatic compound and ammonia can be mixed with the catalyst system in the presence of Water are implemented.

From the examples it can be seen that depending on the specific catalyst material and the reaction conditions used an aromatic diamine product is obtained which is predominantly irieta-phenylenediamine or predominantly ortho-phenylenediamine contains. In general, catalyst masses and reaction conditions favor higher conversion of aromatic monoamines in aromatic diamine, the predominant formation of meta-phenylenediamine; those masses and conditions that lead to a lower conversion lead from aromatic monoamine to aromatic diamine, favor the predominant formation of ortho-phenylenediamine. The incorporation of carbonates or oxides of strontium, magnesium, Gers and the alkaline earth metals and the application of higher catalyst to aromatic monoamine ratios also, as has been observed, favor meta-phenylenediamine formation. A lower amination temperature seems to favor the formation of ortho-phenylenediamine.

In the preferred embodiment of the present invention the aromatic compound to be aminated is aniline. The preferred catalyst composition for this amination comprises a pre-reduced and conditioned nickel / nickel oxide / zirconium oxide / strontium oxide combination. The preferred catalyst composition contains at least 0.9 wt .- ^ elemental nickel

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and has a total surface area of at least 1.35 m / g on.

The reaction is preferably carried out at a temperature in Range from about 250 ° C to about 500 ° C and at a pressure in the range from about 30 atmospheres to about 700 Atmospheres carried out.

The invention is further carried out in the following examples illustrated. Examples 1, 5, 8, 9 »10, 13, 14 and 15 illustrate the predominant production of meta-phenylenediamine; Example 16 illustrates the predominant preparation of ortho-phenylenediamine; and Examples 17 and 18 illustrate the preparation of approximately equal amounts of the ortho- and meta-phenylenediamines.

example 1

Amination of aniline - catalyst composition - Ni / Sr / Zr (1 / 0.05 / 0.3) - ■

In an 8 liter stainless steel beaker, 290.8 g of Ni (N0 _{5) 2} -6H ₂ 0, 10.6 g of Sr (N0 _{3) 2,} 82.8 g of zirconyl nitrate and 3000 ml of distilled water are placed. The salts are dissolved by rapidly stirring the mixture at room temperature. A separate solution is prepared by similarly dissolving -157.2 g (ΝΗ.) ₂ 00, · Ηρ0 in 15ΟΟ ml of distilled water. The carbonate solution is quickly added to the nitrate solution while it is rapidly stirred. The resulting mixture is left to rest for an additional hour at room temperature, then filtered on a filter made of coarse glass frit and finally washed with three 500 ml portions of distilled water. That

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Semi-air dried, green, paste-like material is dried in a circulating air oven at 120 ° C for 17 hours. The oven dried, green solid weighs 158.6 g.

This green, solid material is for the most part ~ 37V75mm "(1/8") toj5.35mm using a mortar and pestle large grains and some grit broken. This material comes in four proportions, as in the following example for specified a proportion, reduced.

A 55.88 cm (22 ") long quartz tube, nominally 2.54 cm in diameter, is loaded with 40.0 grams of the material described above loaded. The tube is arranged in a vertical slot tube furnace. One clad in platinum thermoelectric element is immersed deeply in the lower central part of the bed from the upper part of the tube; * the thermoelectric element is connected to a temperature regulating unit which controls the furnace.

A gas supply line is connected to the lower part of the tube, and a gas mixture of 90 ml of N ₂ and 10 ml of H _? every minute is introduced into the pipe.

The temperature controller is set to 380 ° C and switched on. The bed temperature reached 480 ° C in about 20 minutes, indicating an exothermic reaction that held the temperature above 400 ° C for 22 minutes. During this period, the hydrogen concentration in 10 minutigen intervals of 90 N ₂ / 1O H is ₂ to 75 N _2/25 H ₂ 50 N _2/50 H ₂ 25 N ₂ /? 5 H ₂ up to 100 ml H ₂ / minute elevated. The bed temperature is kept at 380 bis for an additional hour

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400 ° C held, with 100 ml of hydrogen per minute in the Flow into the pipe. The tube contents are cooled to room temperature under a gas flow of 90 ml Np / 10 ml Hp per minute, and the fine to granular, blackish powder is, after js has reached room temperature, in the presence of a A limited amount of air was transferred to an 8 oz (227 g) jar. A certain warming of the hash occurs, after the air has come into contact with the powder. The catalyst weighs 20.7 g.

Analysis: total nickel: $ 68.47; reduced nickel as nickel metal: 28.1? $; the total surface is 74.8 m ² / g.

A 110 ml shaking tube made of mild steel, which is flushed with nitrogen gas, is filled with 20 g of the above-mentioned catalyst, 18.6 g of aniline and 7.2 g of distilled water. The tube is closed and cooled to about -80 ° C in a dry ice box. After the contents have cooled, the tube is alternately evacuated three times by means of a vacuum line and flushed with nitrogen. The tube is then charged with 17 grams of ammonia, sealed and, while moving at 84 30.5 cm (12 ") strokes per minute, under autogenous pressure, which is found to be in the range of 300 to 400 in typical experiments Atmospheres, heated for 15 minutes to 350 ° 0. After cooling to room temperature, the excess ammonia is slowly drained off, and the tube contents are found to contain 1.30 g of phenylenediamines, which corresponds to 6.98 g of phenylenediamines per 100 g of that fed to the reactor aniline corresponds. the distribution of isomers is meta- to 74.5 wt .- ^. 21.8 wt .- $ ortho- and 3 _f 7 wt .- # para-phenylenediamine found.

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Air

Example 2

Amination of aniline - catalyst composition - Ni / Sr / Zr (1 / 0.1 / 0.5) - effect of added water

A solution prepared from 290.8 g of Ni (NO ₃ I _{2 -6H 2} O, 21.2 g of Sr (NO _{3 I 2} , 82.8 g of zirconyl nitrate and 3000 ml of distilled water) is made in the same way as in Example 1 with a Treated solution, which has been prepared by dissolving 163 g of ammonium carbonate in 1500 ml of distilled water. The stirring, filtering and washing of the precipitate is carried out in the same way as in Example 1, and the precipitate is finally washed on the filter with a solution, which contains 10 g of sodium hydroxide in 500 ml of distilled water. The green paste, which is half-dried in air, is dried in a circulating air oven at 102 ° C. for 16 hours. The oven-dried, solid material weighs 165.9 g.

A portion of this material, namely 43.2 g, will be similar Way as described in Example 1, only that the peak temperature is reduced during the exothermic reaction Reached 510 ° C. After cooling the reduced material to room temperature under nitrogen, it becomes in the presence a small amount of air transferred into a glass vessel. The catalyst weighs 25.4 g.

A 110 ml mild steel shaker tube is charged with 18.6 g Aniline, 17 g of ammonia and 20 g of the above catalyst in the same way as described in Example 1, charged. While moving the tube at 84 30.5 cm strokes per minute, the tube is heated to 350 ° C for 7 minutes. When cooling to room temperature and slowly draining the

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Ammonia, it is found that the tubular content contains 0.74 g phenylenediamines, corresponding to 3 _f 97 g phenylenediamines / 100 g initiated aniline.

The experiment is repeated exactly as described above, except that 3 »6.g distilled water is added to the batch will. 1.38 g of phenylenediamines are then obtained, which corresponds to 7.44 g of phenylenediamines per 100 g of aniline introduced.

Example3

Amination of aniline - catalyst composition - Ni / Sr / Zr (1 / 0.2 / 0.3)

A solution prepared by dissolving 290.8 g of Ni (N0 ₃ ) ₂ «6H ₂ 0, 42.3 g of Sr (ND) ₂ and 82.8 g of zirconyl nitrate in 3000 ml of distilled water is produced in the same way as described in Example 1, treated with a solution containing 175.6 g of ammonium carbonate dissolved in 1500 ml of distilled water. The stirring, filtering and washing of the precipitate are carried out as described in Example 1. The green, paste-like material is dried in a circulating air oven at 80 ° C for 16 hours, at the end of which time the solid material weighs 164.2 g.

The solid is for the most part broken up into particles 3.175 ram to 6.35 mm in size and in four portions in the same Way, as described in Example 1, reduced. The maximum temperature observed during the exothermic reaction period is 460 ° C. After cooling to room temperature under nitrogen, four batches are placed in a glass vessel transferred, which contains a limited amount of air.

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The jar is placed in a Fisher blender for 16 hours at room temperature. The catalyst weighs 97 g.

A 110 ml mild steel shaking tube is charged with 40 g of the above-mentioned catalyst, 18.6 g of aniline, 17 g of ammonia and 3 »6 g of distilled water and stirred in the manner described in Example 1 for 7 minutes to 350 ° C heated. After cooling, .the waste k and let the excess ammonia will be that of the pipe content contains 2.27 g phenylenediamines, corresponding to 12.2 g Phenylindiaminen / 100 g filled aniline.

Example 4

Amination of aniline - catalyst composition - Ni / Mg / Zr (1 / 0.2 / 0.3) .

A solution made by dissolving 290.8 g of Ni (NO) p.6H ₂ O, 51.3 g of Mg (NO) ₂ »6H ₂ O and 82.8 g of zirconyl nitrate in 3000 ml of distilled water, is treated in the manner described in Example 1 with a solution which has been prepared by dissolving 176.2 g of ammonium carbonate in 1500 ml of distilled water. The stirring, filtering and washing processes are also carried out in the same way as in Example 1. The green, paste-like material is dried in a circulating air oven for 16 hours, at the end of which time the green solid weighs 180.6 g.

The green pestil is in four portions, as in Example 1 described, reduced. A peak temperature of 470 ° C. is observed during the exothermic reaction period.

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After cooling to room temperature under nitrogen, four batches are made in the presence of a limited amount of air transferred into a 227 g glass vessel, which then overturned on the Fisher mixer overnight will. The charcoal-black, granular to finely powdered catalyst obtained weighs 88.5 g.

A 110 ml mild steel shaking tube is filled with 40 g of the above catalyst, 18.6 g of aniline, 3.6 g of distilled water and 17 g of ammonia charged and in the same As described in Example 1, heated to 350 ° C for 30 minutes with agitation. After cooling down Room temperature shows that the pipe contents are 2.55 g of phenylenediamines or 13.7 g of phenylenediamines / 100 g of filled Contains aniline.

Example 5

Amination of aniline - catalyst composition - Ni / Th (l / 0.05) - effect of water in the batch

A solution made by dissolving 290.8 g of Ni ( _{NO,) 2} «6H ₂ O and 27.6 g of Th (NO,), 6H ₃ O in 3000 ml of distilled water is made according to the same practical instruction , given in Example 1, treated with a solution prepared by dissolving 131.2 g of ammonium carbonate in 1500 ml of distilled water. The stirring, filtering and washing processes are also carried out as indicated in Example 1. D'is green, paste-like material is heated in an oven with circulating air at 92 ° C for 64 hours. The solid obtained weighs 125.2 g.

Part of the oven-dried, hydrous oxides, namely

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98.7 g are reduced in two parts according to the method given in Example 1. The observed during the exothermic reaction period of maximum temperature is 404 ⁰ G. After cooling, the tube contents to room temperature under a flow of 100 ml nitrogen per minute of air is introduced at a rate of 2 ml per minute together with the nitrogen into the pipe. After 55 minutes, the air flow is increased to 5 ml per minute for 1 hour and 44 minutes and then increased to 10 ml per minute for 19 minutes, then to 20 ml per minute for 11 minutes and finally to 40 ml per minute for minutes. The maximum temperature recorded during the reaction with air is. 102 ° C.

The nitrogen and air flows are turned off and the black, granular to finely powdered catalyst (51.9 g) is turned off transferred into a glass vessel that is plugged. There is no temperature increase when the catalyst is in the vessel is transferred.

A 110 ml mild steel shaking tube is charged with 10 g of the above-mentioned catalyst, 18.6 g of aniline and 17 g of ammonia and heated in the same way as in Example 1 to 350 ° C. for 7 minutes with agitation. After cooling to room temperature and releasing the excess ammonia is found that contents of the tube containing 0.55 g phenylenediamines, corresponding to 100 g of aniline charged 2.95 g phenylenediamines, and 81.3 wt. -Fo meta-, 13 »4 Comprises wt. -Io ortho- and 5.3 wt. $ Para-phenylenediamine.

The experiment is repeated exactly as described above, except that 1.8 g of distilled water is added to the batch

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will. 1.23 g of phenylenediamines are then obtained, which corresponds to 6.57 g of phenylenediamines / 100 g of aniline filled in. The product comprises 64.0% by weight fo meta-, 31.1% by weight ortho- and 4> 9% by weight para-phenylenediamine.

Example 6

Amination of aniline - catalyst composition - Ni / U (1 / O «O5) - effect; of water in the batch

A solution which has been prepared from 290.8 g Νχ (Ν0,) ₂ .6Η ₂ 0, 25.1 g UO ₂ (NO,) ₂ .6H ₂ O and 3000 ml of distilled water is, as in Example 1 described, treated with a solution prepared by dissolving 131.2 g of ammonium carbonate in 1500 ml of distilled water. The mixture is stirred, filtered and washed in the manner described in Example 1. The green paste-like material obtained is dried in a circulating air oven at 90 ° C. for 64 hours; the solid, hydrous oxides obtained weigh 123.9 g

A part of the hydrous oxides, namely 104.1 g, is reduced in two parts as described in Example 1. The peak temperature recorded during the exothermic reaction period is 392 ° C.

After cooling the contents of the tube under 100 ml of nitrogen per minute to room temperature, 2 ml of air are added for 2 hours introduced into the nitrogen stream, and then the air stream increased to 10 ml for 16 hours. The maximum temperature read during ventilation is 56 ° C.

The black-brown catalyst obtained weighs 58.2 g. He warms up if it is stored in a glass vessel in the presence of air.

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A 110 ml mild steel shaking tube is filled with 10 g of the above catalyst, 18.6 g of aniline and 17 g Ammonia and heated in the same manner as in Example 1 with agitation at 350 ° C for 7 minutes. To cooling to room temperature and draining off the excess ammonia is found that the drilling contents 0.30 g Phenylenediamine contains what is 1.61 g phenylenediamine / 100 g filled aniline corresponds. When the experiment is repeated, 3 * 6 g of distilled water are added to the batch 0.65 g of phenylenediamines are obtained, which corresponds to 3.57 g of phenylenediamines per 100 g of aniline filled in.

Example 7

Amination of aniline - catalyst composition - (nickel / nickel oxide) - effect of water in the batch

A solution which has been prepared by dissolving 290.8 g of Ni (NO,) ₂ -6H ₃ O in 3OOO ml of distilled water is treated according to the method of Example 1 with a solution which consists of 125.5 g of ammonium carbonate in 1500 * ml of distilled v / ater has been produced. The mixture obtained is, as described in Example 1, stirred, filtered and washed. After drying the green, paste-like material for 64 1/2 hours in an oven with circulating air at 90 ° C., 110 g of solid, water-containing oxides are obtained.

A part of these oxides, namely 89.9 g, is, as described in Example 1, reduced in two parts. i) ie during the The maximum temperature read from the exothermic section of the reduction is 448 ° C. After the tube contents have cooled down to

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At room temperature below 100 ml N ₂ / minute, the gray-black material is transferred into a glass vessel in a limited amount of air, which causes the granular to finely powdered pesticide as well as the glass to heat up.

A 110 ml mild steel shaking tube is filled with 10 g of the catalyst specified above, 18.6 g of aniline and 17 g of ammonia are charged and, as described in Example 1, under Agitation heated to 350 ° C for 7 minutes. After cooling down and venting excess ammonia gas, it is found that the pipe contents contain 0.63 g of phenylenediamines, which is 3 corresponds to> 36 g phenylenediamines / 100 g filled aniline.

When the experiment was repeated with the addition of 1.8 g distilled Water to the batch gives 0.70 g of phenylenediamines, which is 3.76 g of phenylenediamines / 100 g of charged Corresponds to aniline.

Example 8 . ·

Catalyst Composition - Ni / ü (0.25 / 0.05)

A solution is prepared from 72.7 g of Ni (N0 ₃ ) _{2 .6H 2} 0, 25.1 g of UO ₂ (NO ₃ ) _r 6H ₃ O and 750 ml of distilled water, which is prepared in the same way as in Example 1 described, is treated with a solution which has been prepared from 37.6 g of ammonium carbonate in 375 ml of distilled water. The mixture is stirred, filtered and washed as in Example 1, except that 175 ml portions of distilled water are used for washing. After drying the paste-like material for 64 hours at 94 ° C., 27.3 g of solid, water-containing oxides are obtained.

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Most of these hydrous oxides, namely 27.1 g, are reduced in a proportion as described in Example 1. The peak temperature read during the reduction is 470 ° C. After cooling to room temperature under 100 ml nitrogen / minute, 2 ml air per minute is initiated and this "rate is gradually increased over a period of 2 hours to 5 ml, 10 ml, 20 ml and 40 ml increased. The mixture of 100 ml nitrogen / minute and 40 ml of air / minute is bubbled through the tube for 20 minutes and then this flow is turned off. The during The maximum temperature read from this ventilation is 85 ° C. The catalyst, which is black-gray in color, is a granular to fine powder and weighs 17.4 g.

A 110 ml mild steel shaking tube is charged with 10 g of the above-mentioned catalyst, 18.6 g of aniline and 17 g of ammonia and, as described in Example 1, heated to 350 ° C. for 7 minutes. After cooling to room temperature and draining off the excess ammonia, it is found that the pipe contents contain 0.916 phenylenediamines, which corresponds to 4.92 g phenylenediamines / 100 g filled aniline, and 60 wt .- $> meta-, 35 wt .- $ Ortho- and 5 'by weight para-phenylenediamine.

Example 9

Catalyst Composition - Ni / Zn (0.25 / 0.05) effect of water

By dissolving 72.7 g of Ni (NO ^) ₂ * 6H ₃ O and 14.8 g

^) ₂ -6H ₂ O in 750 ml of distilled water, a solution is prepared in the manner described in Example 1 with a solution of 37.7 g of ammonium carbonate in

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375 ml of distilled water is treated. The stirring, Filtration and washing operations are carried out in the same way as in Example 1, except that 175 ml portions of distilled water can be used. The green, paste-like material is circulated in an oven Air dried for 64 hours at 94 ° C. Weigh the solid, water-containing oxides from oven drying 33.0 g.

The water-containing oxides, namely 32.8 g, are reduced in a proportion according to the method of Example 1. the The maximum temperature observed during the reduction is & Ϊ20 ° C.

After cooling to room temperature under 100 ml of nitrogen per minute, 2 ml of air per minute are poured into the nitrogen stream and this feed is gradually increased to 5, 10, 20 and 40 ml / minute over the next 2 hours elevated. The flow of 100 ml N »and 40 ml air / minute is continued for 30 minutes and then switched off. Of the The catalyst obtained, a dark gray, granular to fine powder, weighs 17.3 g.

A 110 ml mild steel shaker tube is charged with 8.5 g of the above catalyst, 18.6 g of aniline and 17 g of ammonia are charged and, as described in Example 1, under Agitation heated to 350 ° C for 7 minutes. After cooling to room temperature and draining off excess ammonia the tube is found to contain 0.63 g of phenylenediamines, which corresponds to 3.39 g of phenylenediamines / 100 g of aniline charged.

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When the experiment is repeated, but 3.6 g of distilled water are added to the batch, 1.17 g of phenylenediamines are obtained, which corresponds to 6.26 g of phenylenediamines / 100 g of aniline filled. The product comprises 55 _} 2 wt .- ^ meta-, 39.8 wt .- ^ ortho- and 5 wt .-% para-phenylenediamine.

Example 10

Catalyst Composition - Ni / Fe (1 / 0.1) Effect of Water on Distribution

From 290.8 g of Ni (NO ₃ ) ₂ -6H ₂ O, 40.4 g of Pe (NO ₃ ), 9H ₂ O, 3000 ml of distilled water, a solution is prepared which, as described in Example 1, with a Solution is treated, which has been prepared from 144 g of ammonium carbonate in 1500 ml of distilled water. The same as in Example 1 is stirred, filtered and washed. The green, paste-like material obtained is dried for 21 1/4 hours at 125 ° C. in a vacuum oven. The solid, hydrous oxides obtained weigh 203 »4 g.

A portion of these oxides, namely 124.4 g, is in two portions reduced according to the method of Example 1, except that the temperature is for 1/2 hour at 100 ° C, 150 ° 0 and 200 ° C and then finally to 400 ° C for 1 hour is set with the hydrogen flowing at a rate of 100 ml / minute.

After cooling to room temperature under 100 ml nitrogen / minute 2 ml of air / minute are introduced into the nitrogen stream, and this supply is gradually increased during the the following 2 hours increased to 5, 10, 20 and 40 ml / minute. For another half an hour, a 100 ml nitrogen / -

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Minute - 40 ml air / minute ~ current passed through the tube. The catalyst obtained, a light to dark gray, granular to finely powdered material, weighs 35.2 g.

A 110 ml mild steel shaking tube is filled with 10 g of the above-mentioned catalyst, 18.6 g of aniline and 17 g of ammonia charged and with agitation as in Example 1

Heated to 350 ° 0 for 7 minutes. After cooling to room temperature and draining the excess ammonia the tube is found to contain 0.67 g of phenylenediamines, which corresponds to 3.61 g of phenylenediamines / 100 g of aniline charged. The phenylenediamines range from $ 69 »$ 8 ortho-, $ 26.6 meta- and 3,6 ^ para-phenylenediamine.

If the experiment is repeated, the batch adds 1.8 g of distilled Adding water gives 0.88 g of phenylenediamines, corresponding to 4.85 g of phenylenediamines / 100 g of aniline filled in. The phenylenediamines comprise 56.1 wt .- ^ meta-, 38.3 wt .- $ ortho- and 5.6% by weight para-phenylenediamine.

Example 11

Catalyst Composition - Ni / Fe (0.5 / 0.05) effect of water

A solution which has been prepared by dissolving 145.4 g of Ni (NO,) p.oELO and 20.2 g of Fe (NO ₃ ) -. 9H_0 in 1500 ml of distilled water is treated with a solution which is prepared according to the Method of Example 1 has been prepared from 72 g of ammonium carbonate in 750 ml of distilled water. Stirring, filtering and washing are carried out in the same manner as in Example 1, except that three 250 ml portions

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distilled water can be used and then finally is washed with a washing liquid consisting of 1 g of phosphoric acid in 250 ml of distilled water. The received Paste is dried in a circulating air oven at 102 ° C for 16 hours. 55.7 g of one are obtained solid, hydrous oxide mixture.

The hydrous oxides are divided into two parts according to the Method of Example 1 reduced with the modification that the temperature is set to 150 ° G for 1/2 hour and that at the end of the reduction the temperature is kept at 350 ° G instead of 380 ° G for 1 hour. The during The maximum temperature observed during the reduction is 432 ° C.

The tube contents are brought to room temperature with 100 ml Np per minute cooled, and then air is blown for 1/2 hour at a rate of 2 ml, 5 ml, 10 ml, 20 ml and supplied 40 ml per minute. The catalyst is poured into a glass vessel as a black-gray, granular to fine powder convicted. It weighs 32.2 g.

A 110 ml mild steel shaking tube is filled with 10 g of the above-mentioned catalyst, 18.6 g of aniline and 17 g of ammonia are charged and, with stirring, as described in Example 1, Heated to 350 ° C for 7 minutes. After cooling down of the tube to room temperature and draining the excess ammonia, it is found that the tube content is 0.94 g Phenylenediamines or 5.02 g phenylenediamines / 100 g filled Contains aniline.

If the experiment is repeated as described above, but 1.8 g of distilled water are added to the batch, 1.58 g are obtained

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Phenylenediamines, corresponding to 8.48 g per 100 g filled Aniline.

Example 12

Catalyst Composition - Ni / Fe (0.5 / 0.3) effect of water

A solution which has been prepared from 145.4 g Ni (NO,) _{g .6H 2} O _1, 121.2 g Pe (NO ₅ ) _{,. 9H 2} O and 1500 ml of distilled water is mixed with a solution of 119, Treated 9 g of ammonium carbonate in 750 ml of distilled water according to the method given in Example 1. This solution is stirred rapidly, heated to 80 ° C and held at 80 ° C for 1 hour; then they are allowed to cool to room temperature. The solution is then filtered and washed as indicated in Example 1, except that 250 ml of distilled water are used for each of the three washes.

The paste-like material is dried in a circulating air oven at 105 ° C for 16 1/4 hours. The received, solid oxides containing water weigh 92.7 g.

The water-containing oxides are reduced in a proportion as described in Example 1, except that the temperature is 1/2 Set at 150 ° C for 1 hour and the final stage of the reduction carried out at 400 ° C instead of 380 ° C for 1 hour will. The maximum temperature observed during the reduction is 492 ° C. After the pipe contents have cooled to room temperature under 100 ml nitrogen / minute, air is introduced at a rate of 5 ml, 10 ml, 20 ml and 40 ml / minute, and each rate is maintained for 1/2 hour before gas flow is turned off.

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-21U170

AD-4508-R

A 110 ml mild steel shaking tube is filled with 10 g of the above catalyst, 18.6 g of aniline and 17 g Ammonia charged and heated with agitation according to the method of Example 1 for 7 minutes at 350 ° G. To cooling the tube to room temperature and draining the excess ammonia you will find that the tube contents Contains 0.83 g phenylenediamines, which corresponds to 4.5 g phenylenediamines / 100 g filled aniline.

If the experiment is repeated, but 2.7 g of distilled water are added to the batch, 0.88 g of phenylenediamines are obtained, corresponding to 4.7 g / 100 g filled aniline.

Example 13 Catalyst Composition - Ni / Ce (1 / 0.2)

A solution made from 290.8 g of Ni (NO, ) _? . 6H ₃ O, 86.9 g of Ce (NO ₅ ), 6H ₂ O and -3000 ml of distilled water has been prepared, as described in Example 1, treated with a solution which was distilled from 15 g of sodium carbonate and 1500 ml Water has been produced. The stirring, filtering and washing are carried out in the same way according to the method of Example 1. The paste-like material obtained is dried in a circulating air oven at 102 ° C. for 64 hours. 185.6 g of solid, water-containing oxides are obtained.

These oxides are in'vier proportions as indicated in Example 1 is reduced, except that the temperature before heating to 400 ° C for 1/2 hour is maintained at ⁰ C for I5O. The reduction is continued for 1 hour at 400 ° C. and then the tube contents are increased under 100 ml nitrogen / minute

- 24 109842/1 968

AD-45O8-H 21 H 170

Ii * ■

Cooled to room temperature. Then air is introduced into the nitrogen stream at a rate of 5 ml, 10 ml, 20 ml and 40 ml / minute each for 1/2 hour. The maximum temperature observed during the ventilation is 66 ° 0. The gray-brown to blue-black, granular to finely powdered catalyst weighs 104 _f 8 g.

A 110 ml mild steel shaking tube is charged with 10 g of the above-mentioned catalyst, 18.6 g of aniline, 2.7 g of distilled water and 17 g of ammonia and stirred, as described in Example 1, for 7 minutes at 350 ° C heated. After cooling the tube to room temperature and releasing the excess ammonia is found that contents of the tube containing 1.37 g of phenylenediamines to give 7 "35 g per 100 g filled aniline corresponds to 69 and _f 9 wt. -Fo meta-, 25» 5 wt .- ^ ortho- and 4 »6 wt. -Fo para-phenylenediamine comprises.

Example 14 "■

Catalyst production by decomposing a nickel compound

2 quartz tubes described in Example 1 are each charged with about 50 g of nickel formate. Nitrogen comes with a Speed of 50 ml / minute sent through the tubes, and the tube contents will slowly increase over the course of 5 hours 380 ° C brought. The tube contents are kept at 380 ° C for 1 hour held and then cooled to 52 ° C and 80 ° 0, at which temperatures 10 ml air / minute for 25 minutes in the nitrogen electricity to be introduced. There is no observable exothermic reaction, and the contents of the tubes, a brown one to gray-black powder that is 28.9. weighs g, is poured into a glass

- 25 1098A2 / 1968

.AB-4508-E. ²¹¹⁴¹⁷ O

vessel transferred, again without any signs of any exothermic reaction.

A 110 ml flu'ßetahl shaking tube is filled with 9 g of des above catalyst, 18.6 g of aniline and 17 g of ammonia are charged, and the Eohr is agitated as in example 1, heated to 350 ° C for 7 minutes. After cooling to room temperature and draining the excess Ammonia is found that the pipe contents 0.73 g phenylenediamines or 3 »90 g phenylenediamines / 100 g filled Contains aniline and 44.8 wt .- ^ meta-, 50.3 wt .- ^ ortho- and 4.9 wt .- ^ para-phenyl diamine comprises.

If the experiment described above is repeated, but 1.8 g of distilled water are added to the batch, one obtains 0.85 g phenylenediamines, which corresponds to 4.58 g / 100 g filled aniline. The phenylenediamines comprise 69.9 wt .- ^ meta-, 25.5 wt% ortho and 4.6 wt% para phenylenediamine.

Example 15

Catalyst - Ni / Ca / Zr (1 / 0.1 / 0.2) ■ »Effect of the temperature during the amination (steered towards meta)

A solution containing 290.8 g Ni (NO ₃ ) ₂ .6H ₂ O, 23.6 g Ca (NQ,) ₂ .H ₂ 0 and 82.8 g zirconium nitrate in 3000 ml of distilled water is, as in Example 1 described, mixed with a solution containing 116 g of sodium hydroxide in 1500 ml of distilled water. The resulting precipitate is filtered, washed and dried in a circulating air oven at about 100 ° G for 16 hours and 10 minutes. 170.4 g of a green pesticide are obtained. This is according to

- 26 109842/1968

2 *

the procedure of Example 1 largely to 3.175 mm Up to 6.35 mm large grains and some grit broken and reduced in two parts with hydrogen. The during The maximum temperature read after the reduction is 405 ° C. The reduced material (111.9 g) is then below 100 ml Cooled nitrogen per minute to room temperature and in Air is transferred into an air-containing vessel, which is stoppered, and pending use in the following experiments stored.

A 110 ml mild steel shaker tube is filled with 18.6 g Aniline, 10 g of the above catalyst and 17 g of ammonia charged; the tube is as in example 1 below Stir heated to 350 ° C for 12 minutes and cooled, and the excess ammonia is drained off.

It is found that the contents of the tube contain 0.525 g of phenylenediamines, which corresponds to 2.82 g / 100 g of aniline filled in. Of the Contents include -50.8 wt .- ^ meta-, 45 wt .- $ ortho- and 4.2 wt .- $ para-phenylenediamine.

If the same experiment is repeated with the modification that 3.6 g of distilled water are added to the batch and the reaction is carried out for 10 minutes at 400 ° C, the tube contents contain 0.522 g of phenylenediamines, which is 2.81 g of phenylenediamines / 100 g corresponds to aniline filled into the tube, and comprises 64.8 $ meta-, 29.5 ° ortho- and 5.7 ° para-phenylenediamine.

Example 16

Catalyst - Ni / Zr (1 / 0.2) - Ba (OH ₂ ) - washing - (directed towards ortho)

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AD-4508-R

A solution of 290.8 g of (Ni (NO) _g .6H ₂ O in 3000 ml of distilled water is mixed with a solution of 107i2 g of NaOH in 1500 ml of distilled water, essentially in accordance with the procedure of Example 1. The precipitate obtained is filtered and washed three times with water. This is followed by a wash with a solution of 15 g of barium hydroxide in 500 ml of distilled water. The paste-like, green precipitate was dried for 16 hours in an oven with circulating air at 102 ° C. The conservation w. tene Green pesticide (173.3 g) is broken up and reduced in two parts as described in Example 1, except that the temperature controller is immediately set to 380 ° C and the last part of the reduction is carried out for 1 hour at 380 ° G, with a hydrogen flow of 100 ml / minute is applied, the reduced mass is cooled to room temperature under 100 ml of nitrogen / minute, the two portions are then blown into an air-containing Eq into the vessel and mixed thoroughly. 59.2 g of a green to black powdery pesticide are obtained.

A 110 ml type Plußstahl shaker tube is charged with 10 g "of the above-mentioned catalyst, 18.6 g of aniline and 17 g ammonia and heated with agitation, as described in Example 1 'under autogenous pressure for 7 minutes at 35O ⁰ C. After After cooling, draining the excess ammonia and opening the tube, it is found that the tube contents contain 0.351 g of phenylenediamines, which corresponds to 1.89 g / 100 g of aniline filled in.

The phenylenediamine isomer distribution is 66.2% by weight ortho-, 1.6% by weight para-, and 37.2% by weight meta-phenylenediamine.

- 28 1098A2 / 1968

AD-4508-R ^; 21H170

Repeat the experiment described above using of 3.6 g of distilled water in the batch, 2.39 g of phenylenediamine / 100 g of aniline filled in is obtained. The ortho ^ isomer is 58.5 #.

In a third experiment, using 5.4 g of distilled water in the batch, 2.80 g of phenylenediamine / 100 g of aniline charged is obtained. The ortho-isomer comprises 61.7 wt. -I * the mixture.

Example 17

Catalyst Ni / NiO (directed towards ortho and meta)

A solution of 290.8 g of Ni (N0_) ₂ .6H ₂ in 3000 ml of distilled water is mixed with a solution of 125.5 g of ammonium carbonate in 1500 ml of distilled water with rapid stirring. The resulting mixture is stirred for an additional hour at room temperature, then filtered, washed with three 500 ml portions of distilled water, and dried in a circulating air oven for 64 1/2 hours at 110.degree.

The dried, green pestilent (110 g) is broken and reduced as in example 1.

When setting the temperature controller to 380 ° C, while 42.8 g of green solid in the reduction tube located, a gas mixture of 90 ml N ₂ / 1O ml of H ₂ per minute introduced in da3 tube. In about 20 minutes, the bed temperature reaches a value in the range of 432-448 ° C, indicating an exothermic reaction that holds the temperature above 400 ° C for about 20 minutes. Meanwhile, the hydrogen

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concentration is increased stepwise at intervals of 10 minutes from 90 N ₂ / H ₂ to 75 1O N ₂ / 25H ₂ at 50 N ₂ / H ₂ 50 to 25 ₂ N / 75 H ₂ up to 100 ml _H? increased per minute. The bed temperature is maintained at 380 ° 0 to 388 ° C for an additional hour with 100 ml Hg per minute flowing into the tube. The material is brought to a temperature of 26 ° C under nitrogen at a rate of 100 ml / minute cooled, and then air is introduced at a rate of 2 ml / minute into the nitrogen stream flowing into the tube for 38 minutes, during which time the bed temperature rises to 36 ⁰ C. The air velocity is then increased to 5 ml / minute for 15 minutes, then to 10 ml / minute for 47 minutes, then to 20 ml / minute for 20 minutes and finally to 40 ml / minute for 30 minutes.

The black, granular to finely powdered catalyst (19.5 g) is transferred into a bottle by air and in front of the Use stored overnight in the following experiment.

A 110 ml mild steel shaking tube that is filled with stickst off gas has been flushed with 10 g of the above catalyst, 18.6 g (0.2 mol) of aniline and 17 g of ammonia charged, heated to 350 ° C for 7 minutes with agitation and cooled, and the ammonia is slowly drained off. It is found that the pipe contents contain 0.63 g of phenylenediamines, which corresponds to 3 »36 g phenylenediamines / 100 g filled aniline. The phenylenediamines include 54.7 wt% ortho-, 4.7 wt% para-, and 40.6 wt% meta-phenylenediamine.

If the experiment is repeated by adding 1.8 g of distilled water to the batch, 0.70 g of phenylenediamines are obtained, corresponding to 3.76 g phenylenediamines / 100 g of the filled

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3 //

Aniline. The phenylenediamines include ortho 60.7 i °, 3.1 ^ S-para and meta-phenylenediamine 36.2 9 ^.

Example 18

Catalyst - Ni / Ti 0 / 0.3) - ( steered according to ortho and meta αϊη)

A slurry of 290.8 g of Ni (N0,) ₂ .6H ₂ 0 and 23.9 g of titanium dioxide in 3000 ml of distilled water is mixed with rapid stirring with 125.5 g of ammonium carbonate in I5OO ml of distilled water. The precipitate obtained is filtered off, washed with water, dried and, as in Example 1, reduced with hydrogen.

A 110 ml river steel shaker tube is filled with 10 g of the above-mentioned catalyst, 18.6 g of aniline and 17 g of ammonia and charged under autogenous pressure for 5 minutes heated to 350 ° C for a long time. The phenylenediamines in the product correspond to -1.04 g / 100 g of aniline filled and comprise 49.4% by weight 5 ^ meta-, 4.4% by weight para- and 46.2% by weight ortho-phenylenediamine.

- 31 1098Λ2 / 1968

Claims (8)

21U170 AD-45O8-R - ^{24 Mar2 1971} Patent claims Process for the preparation of an aromatic diamine, characterized in that a monoamine-substituted aromatic compound, namely an aryl or an alkaryl compound, in the presence of a Uiekel / Kicke1 oxide catalyst composition at a temperature in the range from 150 ° C to 500 ° C and at a pressure in the range of about 10 atmospheres to about 1000 atmospheres with ammonia UI
winnt. reacts and the aromatic diamine obtained 2. The method according to claim 1, characterized in that the temperature is kept in the range from 250 ° C to 500 ° C. 3. The method according to claim 1, characterized in that the pressure in the range of about 30 atmospheres to about Holds 700 atmospheres. 4. The method according to claim 1, characterized in that the nickel / nickel oxide catalyst mass additionally at least an oxide or carbonate of a metal from the group of zirconium, strontium, calcium, magnesium, zinc, iron, titanium, Contains aluminum, silicon, cerium, thorium, uranium and the alkali metals. 5- The method according to claim 4, characterized in that the compound is predominantly a carbonate of a metal, namely strontium, barium, calcium or the alkali metals is. - 32 109 8 42/1968 6. The method according to claim 4, characterized in that the compound is predominantly an oxide of a metal, and made of zirconium, magnesium, zinc, iron, titanium, aluminum, silicon, cerium, thorium or uranium. 7. The method according to claim 1, characterized in that the monoamino-substituted compound is aniline. 8. The method according to claim 1, characterized in that the liickel / nickel oxide catalyst before their
Used in amination by partial reduction of the nickel oxide in a hydrogen atmosphere and then partially oxidized. - 33 109842/1968