DE2003842A1 - Continuous process for the production of organic amines - Google Patents

Description

DR L MAAS

DR. W. PFEIFFER DRF.VORTHENLElTH «

• monk 4 «

mn t * im ·· β ···

Halcon International. Inc .. Hew York, N.Y. V, St.A,

Continuous process for the production of organic amines

Summary.

It will be a continuous process to produce τοη organic amines by amination of the corresponding organic alcohols with ammonia in the presence of a silicon dioxide-aluminum oxide catalyst continuous regeneration of the catalyst described

The invention relates to a continuous process for the preparation of organic amines from organic Alcohols by vapor phase amination of an alcohol with ammonia in the presence of a silica-alumina catalyst with an aluminum oxide content of 35 to 55 pounds based on the total silicon dioxide-aluminum oxide content, which includes the regeneration of the catalyst and the continuation of the vapor phase reaction. In particular concerns the invention entails the preparation of compounds of the aniline type by continuous vapor phase amination.

009131/1181

BATH ORIGINAL

speaking phenolic compounds with ammonia in the presence of the silicon dioxide-aluminum oxide catalyst, the reaction being stopped before the reaction temperature ^{exceeds 57O 0} C, the catalyst is regenerated and the reaction is then continued.

Catalysts used for the amination reactions mentioned above require regular regeneration because carbon-containing coatings are formed on them. The catalyst can be freed from the carbonaceous material by heating in an oxidizing atmosphere. Regeneration has proven difficult for Jedooh. For example, US Pat. No. 3,272,865 describes the use of a silica-alumina catalyst with a content of 10 to 20 Jt> silica or alumina and recommends the use of oxidation metals in such catalysts to facilitate regeneration.

In a continuous process for the production of organic amines from alcohols, silica-alumina catalysts of various compositions have been tested. As expected, all catalysts are deactivated and require regeneration. Unexpectedly, however, not all of these catalyst compositions can be completely up to Their original activity can be regenerated. Complete regeneration is only possible with certain compositions. It has been found that for a continuous process for the preparation of these organic amines using a silicon dioxide-aluminum oxide catalyst, such a catalyst is 35 to 55 % based on aluminum oxide the entire silicon

009831/1911

BATH ORIGINAL

must have dioxide-aluminum oxide content. Bs has shown that this percentage content of aluminum oxide for the regenerability of the catalyst up to its original Activity and thus for the successful development of a continuous economic process is crucial. Silica-alumina catalysts with other compositions "own different abilities to regenerate on their" original Activity, and for some compositions, regeneration to its original activity is practically impossible.

U.S. Patent 3,272,665 stated that silica iumdioxide-alumina compositions with a content From 10 to 20 pounds of silicon dioxide or aluminum oxide are more acidic than catalysts whose composition outside lies within these limits and is therefore more appropriate for the amination reaction are. It has been shown that when the Alumina contents in a silica-alumina catalyst the activity of these catalysts decreases. Hearingly, there is a specific one for a technical process Catalyst composition with the highest initial activity is achieved, the catalyst, its use with the exclusion of a catalyst with lower initial activity is preferred, but surprisingly has been found that a carbon dioxide-aluminum oxide catalyst with a low aluminum oxide content (i.e. old aluminum oxide content less than 25 Jt) iwar is highly active, but that it is so hard to regenerate and actually does not regenerate continuously to its original activity can be. In contrast, a Sllioiuadioxid-alumina catalyst with a content of 35 bit 55 wt. - £ - aluminum oxide, based on the total silicon dioxide-aluminum

009831/1811

BATH

The minium oxide content is easily repeated up to its original Regenerate activity. This result is extraordinarily surprising and unexpected as one normally would / 'kvirt ^ that it would depend on the content of silicon dioxide or Alumina depends on whether a catalyst can be successfully regenerated, and therefore would prompt a catalyst composition to use with the highest initial activity. Although, however, for the purposes of the invention The silica-alumina catalyst used has a lower initial activity than other silica-alumina ^ miniunoxide catalysts that are outside the specified range lie, he is nevertheless in favor of a continuous amination process, in which this catalyst can be reused indefinitely in an economical manner is essential more economical. This is the difference to silicon dioxide-aluminum oxide catalysts with other compositions where the first regeneration is very difficult and further regenerations are practically impossible.

Another essential feature of the invention is that the catalyst must be regenerated before the reaction temperature rises above 570 ° C.

W Za an economical technical process for the preparation of organic amines by reaction of ammonia and an alcohol in the presence of a certain catalyst, regeneration of the catalyst and continuation of the reaction was found. It has also been found that a combination of two essential features is required for this process, namely the use of a silicon dioxide-aluminum oxide catalyst with a content of 35 to 55% by weight of aluminum oxide, based on the total silicon dioxide-aluminum oxide content , and a final temperature before execution

009831/1911

3AD OBtGtNAL

20038A2

. the regeneration of no more than 570 ° C.

The invention therefore relates to an economical and industrial process for the production of an organic amine from its corresponding alcohol with a silica-alumina catalyst with an aluminum oxide content of 35 to 55% by weight, based on the total silicon dioxide Aluminum oxide content at which the catalyst regenerates before the reaction temperature rises above 570 ° C and the process is repeated with this regenerated catalyst. The implementation can be done by repeated regeneration of the catalyst can be continued indefinitely.

The inventive method can by any known procedure for the catalytic amination of an organic Alcohol can be carried out in the vapor phase. The reaction conditions (with the exception of the beginning and Final temperature) the known conditions for vapor phase lamination of phenol or naphthol. The implementation can expediently by initiating a mixed call. from ammonia and alcohol vapor in an externally heated one? Reactor made using a silica-alumina catalyst with an aluminum oxide content of 35 to 55 wt .- #, based on the total silicon dioxide-aluminum oxide content. The gases leaving the reactor are cooled, to condense the amine formed and the unreacted alcohol. The product can take any known measures, e.g. by gas chromatography, distillation or crystallization easily separated.

As a starting material for the purpose according to the invention, it is useful to use any aromatic mono- or polyhydroxy compound

009831/1981

BAD LOCATION

binding can be used. Above all, it can be a connection the formula

(OH)

HO

_L

or

(OH)

II

are used, in which the hydroxy group (s) and the substituents R and R ₁ to Re can be in any position of the phenyl or naphthyl radical.

η and m can mean numbers from 0 to 2, but only one of the symbols η and m has the value 0. R and R ₁ to Rc. can hydrogen atoms. Hydroxy groups, lower alkyl radicals with 1 to 6 carbon atoms, e.g. methyl, ethyl or isopropyl, lower alkoxy groups with the same alkyl radicals as above, phenyl radicals, phenyl-lower alkyl radicals in which the lower alkyl radical can contain 1 to 6 carbon atoms, e.g. methyl, propyl or Ieobutyl, or substituted phenyl-lower-alkyl radicals of the formula

(Lower alkyl) -. /

where Rg and R _{7 can be} hydrogen atoms, hydroxyl groups, lower alkoxy radicals (as above) or lower alkyl radicals (as above), where Jedooh is only one of the beats Rg and R ₇

009831/1911

BAD LOCATION] NAU

can mean a water atom. R can also be a substituted one Denotes a phenyl radical which has substituents Rg and Rr as defined above.

Preferably, R and R ₁ denote water atoms, lower alkyl residues, phenyl residues, hydroxyphenyl residues, phenyl-lower alkyl residues or hydroxyphenyl-lower-alkyl create, where not more than one of the residues R and R _{1 represents} a hydrogen atom, R ₂ to Rc hydrogen atoms or lower alkyl residues, where no more than one of the radicals Rg and R, and no more than one of the radicals R. and R _c denotes a hydrogen atom, and only one of the symbols η and m has a value other than 0.

Some examples of preferred compounds for those of the invention Purposes are phenol, naphthol, lower alkyl naphthols, Dihydroxybenzenes, lower alkylphenol, dihydroxybiphenyls and lower alkyl-bis-hydroxyphenyl ·.

Examples of particularly preferred compounds are phenol, 4,4'-dihydroxybiphenyl _/ o-, m- and p-cr * eol, pyrocatechol, resorcinol, hydroquinone, bis- (4,4'-hydroxyphenyl) methane, bis- (4 , 4'-hydroxyphenyl) propane and naphthol.

The silicon dioxide-aluminum oxide catalyst according to the invention can consist of a naturally occurring mineral, for example kaolinite, illite, ghlorite, montmorillonite, vermiculite or halloysite, of processed natural silicon dioxide-aluminum oxide minerals or of industrially produced silicon dioxide-aluminum oxide. The only essential feature of this catalyst is that it contains 35 to 55 % aluminum oxide, based on the total amount of silicon dioxide

009831/1911

Contains alumina in the catalyst. The catalyst can therefore contain other metal cations, e.g. Iron, alkali or alkaline earth cations, e.g., Na, K or Ca and the like. Level ο the catalyst can use inert substances, e.g. ItgO and solid Contain diluents or combinations of inert ingredients and other metal cations. '. V

In the preferred embodiment of the invention, the Ka.taf'J] lyeator is a hydrated or anhydrous ·· 'Sllloluadloxld ·. Alumina containing no more than trace amounts (ie less than £ 5) of cations. In the preferred embodiment ) the aluminum oxide content (calculated from the total silicon dioxide-aluminum oxide content dt · catalyst ·) is 40 to 50-6. . ., * Jf

The molar ratio of ammonia and alcohol when entering Ata *; * \ Reactor can be 3: 1 to 100: 1, but it is a precautionary measure _H , _r ^: \\ between 5: 1 and 25: 1. Dl · Anfangstemperetur of TM "tsung. '\\ ^ _{i can sweokmä01g swisohen 375 and are 570 ° 0 in ftttarf M can jedooh AUOH lower Starttraperaturtn applied who · _r .J that. For example, the starting temperatures used can be tolebe Its ·. · ^Ι '"·, temperatures which result in a steam reaction under the pressure applied swsokaäBlg swisohen 1.05 and 70 * 9 attt (15 to 1000 psig) and is presugawel · · · ₉ · bl ·>'28.1 atU (125 to 400 p? lg).> ·

The reaction will take place at every desired reaction time stopped up to BU 570 ° C or below and dtr catalyst is regenerated. The reaction is preferably interrupted when the reaction temperature is between 440 and 570 ° 0 »but especially 450 and 500 ° C. The response will be sweckmaa- ... • ig aborted by stopping the loading process. , · (

008831 / 1M1

ORIGINAL INSPH3TED

Regeneration is done to remove carbonaceous material from the catalyst. Any other method for the oxidation of carbonaceous material is suitable for this removal. The regeneration can be carried out by passing oxygen or, preferably, an inert gas containing acid off over the catalyst bed at any initial temperature which is at or above the ignition temperature of the carbonaceous material. The regeneration is controlled in such a way that the surface temperature of the catalytic converter is low enough that the catalytic converter is not damaged. This (temperature is usually ^ about 600 ° C. The temperature control can be achieved by controlling the burning rate, achieved by adjusting the percent oxygen content and the initial temperature of the regeneration. Regeneration einfaoh by continuously passing an inert gas, the off a set Säuerst quantity contains , take place over the catalyst bed at temperatures above the ignition point of the carbon-containing material, but below temperatures that would damage the catalyst. However, the regeneration is preferably carried out as follows slner parts related to yolu

-1 i

Set speed from 5 to 5000 h and preferably 300 '

displaced to 1000 h "is then reduced the reaction temperature to about 450 ° C and passes up to 20.8 f> oxygen, preferably 2 -. 5, I ₁ / with a related vorumenteile gas Durohsatzgeschwindig-

, Ksit of about 200 hours to 1,000 ^"1 over the catalyst. Then, the temperature at a rate at which the oxygen content in the exiting GasΠ9 Ψ preferably, is, however, maintained at about 2 to 3%, slowly to about 470 to 55O ⁰ C and preferably increased from 490 to 510 ° C. The temperature is increased

009131/1111

¹ ORIGINAL BATHROOM

again lowered to approximately the initial temperature of the regeneration and the prosentic content of supplied oxygen is increased to 4 to 6 1 * at a rate at which the oxygen content in the outflowing gas is kept at about 2 to 4 ». Finally, the temperature is cooled to about 450 ° C. and air is introduced, while the temperature is increased to 490 to 510 ° C. at such a rate that oxygen is present in the outflowing gas. The catalyst is then ready to continue the amination reaction. The same procedure can be carried out without difficulty in the case of overprinting, the same general range for the oxygen partial pressure being adhered to, as given in the explanation above.

Examples 1 and 2 are intended to show that a silicon dioxide-alurainium oxide catalyst with a percentage aluminum oxide content outside the limits according to the invention cannot easily be regenerated to its initial activity and that after repeated regeneration the catalyst activity continuously decreases. These catalysts are therefore not suitable for a continuous reaction for which continuous regeneration is required. In contrast, Examples 3, 4 and 5 show "that the catalyst composition according to the invention can always be successfully regenerated to its original activity and is therefore extremely suitable for a continuously carried out reaction for which continuous regeneration is required"

The extent of catalyst regeneration is measured by whether the implementation after each regeneration at an initial temperature of the reaction ^^ e ^ ef ^^ anis ^ smperatur of the reaction as close as when starting naoh the previous one

009831/1!

BATH

Regeneration, while practically the same Umeates upright is obtained. Aue example 1 can be seen clearly, for example, that after each regeneration the sum start required initial temperature is higher than the initial temperature at the start after each previous regeneration · In example 1, when the reaction is started, a temperature of 380 ° C is required to achieve a conversion of 94.9 *. Hit progressing implementation bus · Alt reaction temperature be increased so that practically the same umeate is obtained. Haoh the first regeneration is the initial reaction temperature for the new cycle is 400 ° C - 20 ° G higher than the previously required temperature. As implementation progresses with several regenerations, it increases the initial temperature of the conversion after each regeneration at. This increase in the reaction temperature clearly shows that the activity of the catalyst decreases with time and cannot be regenerated to the original activity. In contrast, the catalyst composition shows According to the invention (Examples 3 »4 and 5) it is clear that the catalyst returns to its original state after each regeneration Activity gained. This fact appears when comparing the initial temperature for the start of the reaction every regeneration in appearance. In example 3, the initial temperature is 420 ° C. and after every regeneration is the initial temperature of the reaction to achieve the same conversion is also 420 ° C. In addition, the temperature limits for every cycle after every regeneration practically the same, while in Example 1 the temperature limits near each regeneration moving closer to the top.

The following procedure was used for each example.

00S831 / 19I1

BAO ORIGINAL

a) feeding syatem

A high pressure boom that contains ammonia and with a dip tube is placed in a constant temperature bath of 42 ° C. The bomb pressure under these conditions is about 33.4 atU (475 psig). Aue the cylinder will liquid ammonia removed and passed through a cooler, a Doeierrotameter and duroh a preheating evaporator, in which the temperature is increased to about 225 ° C. This stream of ammonia is mixed with phenol vapor before it enters the reactor mixed. Phenol is pumped with a positive displacement pump through a preheating evaporator in which the temperature of the Phenol via its condensation point at. Reaktlonsdruok, (about 320 ° C) is increased.

b) reactor system

* The reactor consists of a carbon steel pipe with 3 m (10 ') χ 2.5 om (1 ^N ) χ 14 BWO Dae pipe is illuminated from the outside by means of a fine circumferential sales sleeve of high temperature.

c) Collection systems

The gases leaving the reactor are cooled to 70 ° C. in order to condense practically all of the aniline and unreacted phenol W. The exhaust gases are drawn off from the system and analyzed for their residual product content. The condensed product is also analyzed by OaeChromatography using conventional gas chromatographic methods. The material balance for the organic matter amounts to almost 100 verifiable i> when you compare the introduced into the reactor phenol and the products obtained.

The following examples show that an amination reaction with continuous regeneration of the catalyst

009831/1981

BATH ORIGINAL

Can be carried out if the catalyst composition contains about 35 to 55 aluminum oxide, based on the total Silir ^J " is possible when using catalysts in which the aluminum oxide content is outside these limits. It can be seen that in Examples 1 and 2 the catalyst cannot simply be regenerated, while in Examples 3, 4 and 5 the catalysts regain their original activity after each regeneration.

The selectivity to aniline in all examples is more than 90 MoI- *.

The regeneration in Examples 1 to 5 is carried out as follows.

Regeneration process

The following measures are implemented for the regeneration of the catalytic converter. ■ guided.

1. The supply of phenol is interrupted ^

2. The reactor pressure is lowered to atmospheric pressure.

3. Adsorbed organic matter becomes nitrogen gas through the use of nitrogen gas displaced with a Durohsatz enjoyment of 300 h ".

4. The temperature is reduced to 450 ° C and 2 £ oxygen are introduced with a Durohsatzgeschwindigkeit of about 1,000 h "over the catalyst. The temperature is slowly at a speed at which the oxygen content in the exiting Gasstrum about 1.5 1 » Is held, increased to 500 ° 0.

009831/1991

The temperature is reduced to 450 C and the oxygen content in the feed is increased to 5 Ί » . The temperature is increased again to 500 ° C at a rate at which the oxygen content in the effluent gas is maintained at about 4.596. The reactor is cooled to 450 ° C and air is introduced while the temperature is increased to 500 ° C at a rate at which oxygen remains in the effluent gas.

The catalyst is now ready to resume aniline production.

example

Catalyst: silica-alumina with 13? C alumina

Conditions: Catalyst bed: 254 cm (100 ")

hourly Durometer heat rate (liquid volume) 0.058 hours "" ¹

Joint operation (hours)

31 123 180

1. Regeneration

184 309

2. Regeneration

340 386 438

.3. Regeneration

NH ₃ / phenol: pressure:

Cycle duration (hours)

31 123 180

4 129

31

77

129

20: 1

16.9 kg / om ² (240 pels)

Tempera door, ⁰ C

380
390
400

400
408

400
410
421

Phenol conversion (5t)

94.9 94.3 94.5

94.9 94.8

94.6 94.6 95.6

009831/1981

Total operation
(Hours) Cycle duration
(Hours) 2 tempera
door. ⁰ O i Fhenolumsati 462
478
490
53β
568 24
40
52
100
130 405
421
425
435
445 87.2
^) V EL
Al C
* 4 * eX 1 ■ 4. Regeneration
tion · * example

Example 1 is repeated with the exception that the catalyst used is from a different manufacturer, but also contains 13 % aluminum oxide. Practically the same results are obtained after a lapse of 580 hours and at a temperature of 40 ° g. Regeneration * does not increase the catalyst activity. ^;

example Silicon dioxide-aluminum oxide, 45 % aluminum oxide Conditionsι Catalytic converter bed 254 or above (100 ")

Stttndllohe throughput speed (riüesigYOlumen) 0.058 hours. " ⁷

NH./fhenolt 20: 1

Pressure! 16.9 kg / o « ² (240 peia)

009831/1911

ORIGINAL INSPKiTED

Gesaratbetrieb
(Hours) 42
130
248 Cycle duration
(Hours) Tempera"
door. ⁰ O Phenolumaats
(*) Regeneration
tion 42
130
248 420
438
458 96.8
95.2
94.9 ' 1. 266
360
442
459 f
' I *' Regeneration
tion 18th
112
194
211 420
441
454
458 95.1 /
95.1.
94.5
95.1 2. 479
569
644
683 Regeneration
tion 20th
110
185
224 420
459
451
457 95.8
94.9
94.1
94.8 3. 705 22nd 420 94.9

Likewise, when using (equivalent amounts, based on the hydroxy point ion) of '·>; Naphthol, /? - laphthol, 4,4'-dihydroxybiphenyl, bending (4,4'-hydroxyphenyl) -prop *> n, Bi8- (4.4 ^f hydroxyphenyl) ethane, o-cresol, i- Methyl-2-naphthol, ΐ, θ-naphthalenomol, o-butylphenol, 2,6-dlaethoxyphenol, 2-methoxy-4-ethylphenol, m-hydroxybiphenyl, brentoatechol or pyrogallol instead of the phenols used above, the corresponding amino compounds are obtained by repeated generations '.. "-'<

Example 4 ...

The procedure of Example 3 is repeated with a "3ilioiu" dioxide-aluminum oxide from another manufacturer (45 % aluminum oxide). The cycles give practically the | Ielohen values as in Example 3 · »

009831/19!

ORIGINAL INSPECTED

Likewise, when the procedure of Example 3 is repeated with a pilicium dioxide-aluminum oxide catalyst, the 35, 40, 50 ^v **. I contains 55 »alumina, the silica Aluminiuraoxids (45 1» alumina) of Example 3 anateile virtually achieves the same results.

Example 5

The procedure of Example 3 is repeated with a silica-alumina catalyst having an alumina content of 45 i 'with the exception Dafi the phenol and ammonia Beschiekungsgesohwindigkeiten be reduced to half, so that temperatures and cycle times as in Examples 1 and 2 result. As can be seen from the following example, it is again possible to regenerate catalysts with a high aluminum oxide content.

Conditions:

Overall operation
(Hours,)

16

89
191
246
320
445

1 · regeneration

469

Catalyst bed} 254 om (100 ")

hourly Throughput speed (Liquid volume): 0.029 3td. ~~

NH ^ / phenol: 20: 1

Pressure:

Cycle duration (hours)

89 191 246 320 445

Temperature ⁰ C

402 '.' 398 404 406 418 433.

401

16.9 kg / cm ² (240 psia) phenol conversion

96.7 94.6 93.4 93.8 94 * 4 94.9

95.8

009831/1911

Claims (5)

Patent claims 1./Process for the production of organic amines from alcohols the formula (CB) n or B, (0H) m where η and m are numbers from 0 to 2, but only one of the symbols η and m is O ₁ and R and R ₁ to Re are hydrogen atoms, hydroxy groups, lower alkyl radicals, lower alkoxy radicals, phenyl radicals, phenyl lower alkyl radicals, substituted phenyl lower alkyl radicals of the formula (Lower alkyl) - / ^ \ N 2 ^ R _? wherein Rg and R _{7 represent} hydrogen atoms, hydroxyl groups or lower alkoxy groups, but only one of the radicals Έλ and R _{7 is} a hydrogen atom, or substituted phenyl radicals of the formula. , R mean, wherein R ₆ and R _{7 are} as defined above, characterized in that (a) ammonia in the vapor phase 009831/19! the organic alcohol in the presence of a silicon dioxide. Alumina catalyst with an aluminum oil content from 55 to 55 wt .-%, based on the total silica -Aluminium oxide content, continuously converted and thereby continuously generates the organic amine; (b) the reaction stops before the reaction temperature If it exceeds 570 ° 0, (c) the catalyst is regenerated and (d) this reaction sequence is continuously repeated. 2. The method naoh claim 1, characterized by da8 is used in step (a) the reaction of a Anfangetemperatur f 400 to 450 ° C applies a catalyst having a AIuminiumoxldgehalt of 40 to 50 Qew.- £ and in step (b) the reaction at a temperature between 44O ⁰ C and 570 ° C abbriohts. 3. The method according to claim t or 2, characterized in that that one has an alcohol of the formula ' used, in which R is a hydrogen atom, tins hydroxyl group, a lower alkyl radical, a Phenylreet, a Hydroxyphenylreet or a methyl-lower alkyl radical of the formula (lower alkyl) means where Rg is a hydrogen atom, a hydroxyl group, a lower alkyl radical or a lower alkoxy group. 009831/1911 4. The method according to claim 1 or 2, characterized in, that you can get an alcohol of the formula used, in which Rp is a hydrogen atom, a lower one
Denotes an alkyl radical or a lower alkoxy group. 5. The method according to claim 1 or 2, characterized in that that one as alcohol is phenol, bisphenol, OC-naphthol, Bi- (4,4'-hydroxyphenyl) propane or bis (4,4, '- hydroxyphenyl) methane used. 009831 / 1M1