WO1996036600A1 - Titanium dioxide-catalysed cyclisation in the liquid phase of 6-amino caproic acid nitrile to caprolactam - Google Patents

Titanium dioxide-catalysed cyclisation in the liquid phase of 6-amino caproic acid nitrile to caprolactam Download PDF

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Publication number
WO1996036600A1
WO1996036600A1 PCT/EP1996/001891 EP9601891W WO9636600A1 WO 1996036600 A1 WO1996036600 A1 WO 1996036600A1 EP 9601891 W EP9601891 W EP 9601891W WO 9636600 A1 WO9636600 A1 WO 9636600A1
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Prior art keywords
titanium dioxide
caprolactam
liquid phase
water
content
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Application number
PCT/EP1996/001891
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German (de)
French (fr)
Inventor
Eberhard Fuchs
Tom Witzel
Klemens Flick
Original Assignee
Basf Aktiengesellschaft
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Publication date
Priority to SK1548-97A priority Critical patent/SK154897A3/en
Priority to JP8534516A priority patent/JPH11505230A/en
Priority to AU58147/96A priority patent/AU700098B2/en
Priority to BR9608470A priority patent/BR9608470A/en
Priority to MX9708676A priority patent/MX9708676A/en
Priority to NZ308485A priority patent/NZ308485A/en
Priority to PL96323389A priority patent/PL323389A1/en
Priority to EA199700402A priority patent/EA199700402A1/en
Priority to HU9801131A priority patent/HU220356B/en
Priority to EP96919687A priority patent/EP0815077A1/en
Application filed by Basf Aktiengesellschaft filed Critical Basf Aktiengesellschaft
Publication of WO1996036600A1 publication Critical patent/WO1996036600A1/en
Priority to BG102027A priority patent/BG102027A/en
Priority to NO975268A priority patent/NO307964B1/en

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D201/00—Preparation, separation, purification or stabilisation of unsubstituted lactams
    • C07D201/02—Preparation of lactams
    • C07D201/08—Preparation of lactams from carboxylic acids or derivatives thereof, e.g. hydroxy carboxylic acids, lactones or nitriles

Definitions

  • the present invention relates to a new process for the preparation of cyclic lactams by reacting aminocarbonitriles with water in the presence of catalysts.
  • US Pat. No. 2,301,964 relates to the uncatalyzed conversion of 6-aminocapronitrile to caprolactam in aqueous solution at 285 ° C. The yields are below 80%.
  • FR-A 2 029 540 describes a process for the cyclization of 6-aminocapronitrile to caprolactam by means of homogeneous metal catalysts from the zinc and copper group in aqueous solution, with caprolactam being obtained in yields of up to 83%.
  • caprolactam being obtained in yields of up to 83%.
  • the complete separation of the catalyst from the valuable product caprolactam poses problems since this forms complexes with the metals used.
  • the object of the present invention was therefore to provide a process for the preparation of cyclic lactams by reacting aminocarbonitriles with water which does not have the disadvantages described above.
  • the starting materials in the process according to the invention are aminocarbonitriles, preferably those of the general formula I.
  • n and m can each have the values 0, 1, 2, 3, 4, 5, 6, 7, 8 and 9 and the sum of n + m is at least 3, preferably at least 4.
  • R 1 and R 2 can in principle be substituents of any kind, it should only be ensured that the desired cyclization reaction is not influenced by the substituents.
  • R 1 and R 2 are independently Ci-C ⁇ -alkyl or C 5 -C 7 cycloalkyl groups or C 6 -Ci 2 ⁇ aryl groups.
  • Particularly preferred starting compounds are aminocarboxylic acid nitriles of the general formula
  • m has a value of 3, 4, 5 or 6, in particular 5.
  • the starting compound is 6-aminocaproic acid nitrile.
  • the reaction is carried out in the liquid phase at temperatures of generally 140 to 320 ° C, preferably 160 to 280 ° C; the pressure is generally in the range from 1 to 250 bar, preferably from 5 to 150 bar, care being taken that the reaction mixture under the conditions used is predominantly, i.e. without the catalyst present in the solid phase, is liquid.
  • the residence times are generally in the range from 1 to 120, preferably 1 to 90 and in particular 1 to 60 minutes. In some cases, dwell times of 1 to 10 minutes have proven to be completely sufficient.
  • At least 0.01 mol, preferably 0.1 to 20 and in particular 1 to 5 mol, of water are used per mol of aminocarbonitrile.
  • the aminocarbonitrile is advantageously in the form of a 1 to 50% by weight, in particular 5 to 50% by weight, particularly preferably 5 to 30% by weight solution in water (in which case the solvent is also the reactant) or used in water / solvent mixtures.
  • solvents are alkanols such as methanol, ethanol, n- and i-propanol, n-, i- and t-butanol and polyols such as diethylene glycol and tetraethylene glycol, hydrocarbons such as petroleum ether, benzene, toluene, xylene, lactams such as pyrrolidone or caprolactam or alkyl-substituted lactams such as N-methylpyrrolidone, N-methylcaprolactam or N-ethylcaprolactam and carboxylic acid esters, preferably called carboxylic acids having 1 to 8 carbon atoms.
  • Ammonia can also be present in the reaction.
  • Mixtures of organic solvents can of course also be used.
  • Mixtures of water and alkanols in a water / alkanol weight ratio of 1 to 75 to 25 to 99, preferably 1 to 50 50 to 99 have proven to be particularly advantageous in some cases.
  • the process according to the invention is carried out in the presence of titanium dioxide catalysts which have a rutile content in the range from 0.1 to 95, preferably from 1 to 90% by weight and an anatase content in the range from 99.9 to 5, preferably from 99 to 10 wt .-%, each based on the total content of titanium dioxide.
  • the reaction is carried out in a fixed bed, the catalysts being used in the form of strands or tablets, the tablets and strands preferably having a diameter between 1 and 10 mm.
  • titanium dioxide powder which already has the desired content of anatase and rutile or which is obtained by pyrolysis either starting from a pure anatase modification or a mixed form is used
  • Anatase and rutile phases or a mixture of pure anatase and rutile modifications are obtained by using the appropriate temperature and residence time (both are known to the person skilled in the art, for example from Catalysis Today 14, (1992) 225-242). pyrolyzed until the desired anatase to rutile ratio is reached.
  • Corresponding powders are available on the market, for example the titanium dioxide powders P25® (20 to 30% by weight of rutile and 80 to 70% by weight of anatase) from Degussa as well as S150® and S140® (each 100% by weight). % Anatas) by Finti-Kemira.
  • the titanium dioxide can be used as such or as a supported catalyst, whereby it can usually be applied to a mechanically and chemically stable support, usually with a high surface area.
  • the titanium dioxide can have been produced by precipitation from aqueous solutions, e.g. after the sulfate process or by other methods such as the pyrogenic production of fine titanium dioxide powders, which are commercially available.
  • the rutile / anatase-containing titanium dioxide can be mixed with other oxides such as aluminum oxide, zirconium oxide or cerium oxide.
  • oxides or their precursor compounds which can be converted into the oxides by calcining, can be prepared from solution, for example, by co-precipitation. In general, a very good distribution of the two oxides used is obtained.
  • the oxide or Precursor mixtures can also be precipitated by precipitation of one oxide or precursor in the presence of the second oxide or precursor, which is present as a suspension of finely divided particles.
  • Another method consists in mechanical mixing of the oxide or precursor powder, this mixture being able to be used as a starting material for the production of strands or tablets.
  • a ceramic support can be coated with titanium dioxide in a thin layer by hydrolysis of titanium isopropylate or other Ti alkoxides.
  • Another suitable compound is TiCl.
  • Suitable carriers are powders, extrudates or tablets of titanium dioxide itself or other stable oxides such as silicon dioxide. The carriers used can be designed to be macroporous in order to improve the mass transport. It is important that care is taken in the pyrolysis of the titanium dioxide that both rutile and anatase phases occur in the above-mentioned areas.
  • the process according to the invention gives cyclic lactams, in particular caprolactam, in high yield with good selectivities and good constancy of the catalyst activity.
  • a solution of 6-aminocapronitrile (ACN) in water and ethanol was introduced into the in a heated tubular reactor of 25 ml (diameter 6 mm; length 800 mm) filled with titanium dioxide in the form of tablets or strands at 100 bar weight ratios given in the table.
  • the product stream leaving the reactor was analyzed by gas chromatography. The results are also shown in the table. table
  • Example catalyst form sulfate content rutile anatase BET A U S [%] [%] [m / g]

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  • Organic Chemistry (AREA)
  • Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
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Abstract

Production of cyclic lactams by the reaction of amino carboxylic acid nitriles with water, performed in the liquid phase in the presence of heterogeneous catalysts based on titanium dioxide with a rutile content in the range from 0.1 to 95 wt.% and an anatase content in the range from 99.9 to 5 wt.% in relation to the total titanium dioxide content.

Description

TITANDIOXIDKATALYSIERTE CYCLISIERUNG IN FLÜSSIGER PHASE VON 6-A IN0CAPR0NSAURENITRIL ZU CAPROLACTAMTITANIUM DIOXIDE CATALYZED CYCLIZATION IN LIQUID PHASE FROM 6-A IN0CAPR0NSAURENITRILE TO CAPROLACTAM
Beschreibungdescription
Die vorliegende Erfindung betrifft ein neues Verfahren zur Her¬ stellung von cyclischen Lactämen durch Umsetzung von Aminocarbon- säurenitrilen mit Wasser in Gegenwart von Katalysatoren.The present invention relates to a new process for the preparation of cyclic lactams by reacting aminocarbonitriles with water in the presence of catalysts.
Aus der US-A 4 628 085 ist die Umsetzung von 6-Aminocapronsäure- nitril mit Wasser in der Gasphase an saurem Kieselgel bei 300°C bekannt. Als Produkt der quantitativ verlaufenden Umsetzung wird mit einer anfänglichen Selektivität von 95 % Caprolactam er¬ halten, doch ist ein schneller Produktivitäts- und Selektivitäts- rückgang festzustellen. Ein ähnliches Verfahren wird in derThe reaction of 6-aminocaproic acid nitrile with water in the gas phase on acidic silica gel at 300 ° C. is known from US Pat. No. 4,628,085. An initial selectivity of 95% caprolactam is obtained as the product of the quantitative reaction, but a rapid decrease in productivity and selectivity can be observed. A similar procedure is used in the
US-A 4 625 023 beschrieben, nach der ein hochverdünnter Gasstrom aus 6-Aminocapronsäurenitril, Adipinsäuredinitril, Ammoniak, Wasser und Trägergas über ein Kieselgel- und ein Kupfer/Chrom/ Barium-Titanoxid Katalysatorbett geleitet wird. Bei 85 % Umsatz wird Caprolactam mit einer Selektivität von 91 % erhalten. Auch hier ist eine schnelle Katalysatordesaktivierung zu beobachten.US Pat. No. 4,625,023, according to which a highly diluted gas stream of 6-aminocapronitrile, adiponitrile, ammonia, water and carrier gas is passed over a bed of silica gel and a copper / chromium / barium titanium oxide catalyst bed. With 85% conversion, caprolactam is obtained with a selectivity of 91%. Rapid catalyst deactivation can also be observed here.
Gegenstand der US-A 2 301 964 ist die nicht katalysierte Um¬ setzung von 6-Aminocapronsäurenitril zu Caprolactam in wäßriger Lösung bei 285°C. Die Ausbeuten liegen unter 80 %.US Pat. No. 2,301,964 relates to the uncatalyzed conversion of 6-aminocapronitrile to caprolactam in aqueous solution at 285 ° C. The yields are below 80%.
Die FR-A 2 029 540 beschreibt ein Verfahren zur Cyclisierung von 6-Aminocapronsäurenitril zu Caprolactam mittels homogener Metall¬ katalysatoren aus der Zink- und Kupfergruppe in wäßriger Lösung, wobei Caprolactam in Ausbeuten bis zu 83 % erhalten wird. Die vollständige Abtrennung des Katalysators vom Wertprodukt Capro¬ lactam bereitet jedoch Probleme, da dieses Komplexe mit den ver¬ wendeten Metallen bildet.FR-A 2 029 540 describes a process for the cyclization of 6-aminocapronitrile to caprolactam by means of homogeneous metal catalysts from the zinc and copper group in aqueous solution, with caprolactam being obtained in yields of up to 83%. However, the complete separation of the catalyst from the valuable product caprolactam poses problems since this forms complexes with the metals used.
Aufgabe der vorliegenden Erfindung war es daher, ein Verfahren zur Herstellung cyclischer Lactame durch Umsetzung von Amino- carbonsäurenitrilen mit Wasser zur Verfügung zu stellen, das die vorstehend beschriebenen Nachteile nicht mit sich bringt.The object of the present invention was therefore to provide a process for the preparation of cyclic lactams by reacting aminocarbonitriles with water which does not have the disadvantages described above.
Diese Aufgabe wird erfindungsgemäß dadurch gelöst, daß die Um¬ setzung in flüssiger Phase in Gegenwart heterogener Katalysatoren auf der Basis von Titandioxid mit einem Rutil-Gehalt im Bereich von 0,1 bis 95 Gew.-% und einem Anatas-Gehalt von 99,9 bis 5 Gew.-%,. jeweils bezogen auf den Gesamtgehalt an Titandioxid, durchgeführt wird. Bevorzugte Ausführungsformen des erfindungsgemäßen Verfahrens sind den Unteransprüchen zu entnehmen.This object is achieved according to the invention in that the reaction in the liquid phase in the presence of heterogeneous catalysts based on titanium dioxide with a rutile content in the range from 0.1 to 95% by weight and an anatase content of 99.9 up to 5% by weight. in each case based on the total content of titanium dioxide. Preferred embodiments of the method according to the invention can be found in the subclaims.
Als Ausgangsstoffe im erfindungsgemäßen Verfahren werden Amino- carbonsäurenitrile, vorzugsweise solche der allgemeinen Formel IThe starting materials in the process according to the invention are aminocarbonitriles, preferably those of the general formula I.
Figure imgf000004_0001
Figure imgf000004_0001
eingesetzt, wobei n und m jeweils die Werte 0, 1, 2, 3, 4, 5, 6, 7, 8 und 9 haben können und die Summe aus n + m mindestens 3, vorzugsweise mindestens 4 beträgt.used, where n and m can each have the values 0, 1, 2, 3, 4, 5, 6, 7, 8 and 9 and the sum of n + m is at least 3, preferably at least 4.
R1 und R2 können prinzipiell Substituenten jeglicher Art sein, wobei lediglich sichergestellt sein sollte, daß die gewünschte Cyclisierungsreaktion durch die Substituenten nicht beeinflußt wird. Vorzugsweise sind R1 und R2 unabhängig voneinander Ci-Cβ-Alkyl- oder C5-C7-Cycloalkylgruppen oder C6-Ci2~Arylgruppen.R 1 and R 2 can in principle be substituents of any kind, it should only be ensured that the desired cyclization reaction is not influenced by the substituents. Preferably R 1 and R 2 are independently Ci-Cβ-alkyl or C 5 -C 7 cycloalkyl groups or C 6 -Ci 2 ~ aryl groups.
Besonders bevorzugte Ausgangsverbindungen sind Aminocarbonsäure- nitrile der allgemeinen FormelParticularly preferred starting compounds are aminocarboxylic acid nitriles of the general formula
H2N—(CH2)rπ—C=NH 2 N— (CH 2 ) rπ-C = N
wobei m einen Wert von 3, 4, 5 oder 6, insbesondere 5 aufweist. Für m = 5 ergibt sich als Ausgangsverbindung 6-Aminocapronsäure- nitril.where m has a value of 3, 4, 5 or 6, in particular 5. For m = 5, the starting compound is 6-aminocaproic acid nitrile.
Nach dem erfindungsgemäßen Verfahren werden die vorstehend be- schriebenen A inocarbonsäurenitrile mit Wasser in flüssiger Phase unter Verwendung heterogener Katalysatoren zu cyclischen Lactämen umgesetzt. Bei Verwendung von Aminocarbonsäurenitrilen der Formel I erhält man die entsprechenden cyclischen Lactame der Formel II
Figure imgf000005_0001
In the process according to the invention, the amino carboxylic acid nitriles described above are reacted with water in the liquid phase using heterogeneous catalysts to form cyclic lactams. When using aminocarbonitriles of the formula I, the corresponding cyclic lactams of the formula II are obtained
Figure imgf000005_0001
wobei n, m, R1 und R2 die vorstehend genannte Bedeutung haben. Besonders bevorzugte Lactame sind solche, in denen n = 0 ist und m einen Wert von 4,5 oder 6 hat, insbesondere 5 (im letzteren Fall erhält man Caprolactam) .where n, m, R 1 and R 2 have the meaning given above. Particularly preferred lactams are those in which n = 0 and m has a value of 4.5 or 6, in particular 5 (in the latter case, caprolactam is obtained).
Die Umsetzung wird in flüssiger Phase bei Temperaturen von im allgemeinen 140 bis 320°C, vorzugsweise 160 bis 280°C, durch¬ geführt; der Druck liegt im allgemeinen im Bereich von 1 bis 250 bar, vorzugsweise von 5 bis 150 bar, wobei darauf zu achten ist, daß das Reaktionsgemisch unter den angewandten Bedingungen zum überwiegenden Teil, d.h. ohne den in fester Phase vorliegen¬ den Katalysator, flüssig ist. Die Verweilzeiten liegen im allge¬ meinen im Bereich von 1 bis 120, vorzugsweise 1 bis 90 und ins¬ besondere 1 bis 60 min. In einigen Fällen haben sich Verweilzei¬ ten von 1 bis 10 min als völlig ausreichend erwiesen.The reaction is carried out in the liquid phase at temperatures of generally 140 to 320 ° C, preferably 160 to 280 ° C; the pressure is generally in the range from 1 to 250 bar, preferably from 5 to 150 bar, care being taken that the reaction mixture under the conditions used is predominantly, i.e. without the catalyst present in the solid phase, is liquid. The residence times are generally in the range from 1 to 120, preferably 1 to 90 and in particular 1 to 60 minutes. In some cases, dwell times of 1 to 10 minutes have proven to be completely sufficient.
Pro mol Aminocarbonsäurenitril werden im allgemeinen mindestens 0,01 mol, vorzugsweise 0,1 bis 20 und insbesondere 1 bis 5 mol Wasser eingesetzt.In general, at least 0.01 mol, preferably 0.1 to 20 and in particular 1 to 5 mol, of water are used per mol of aminocarbonitrile.
Vorteilhaft wird das Aminocarbonsäurenitril in Form einer 1 bis 50 gew.-%igen, insbesondere 5 bis 50 gew.-%igen, besonders vor¬ zugsweise 5 bis 30 gew.-%igen Lösung in Wasser (wobei dann das Lösungsmittel gleichzeitig Reaktionspartner ist) oder in Wasser/ Lösungsmittel-Gemischen eingesetzt. Als Lösungsmittel seien bei- spielhaft Alkanole wie Methanol, Ethanol, n- und i-Propanol, n-, i- und t-Butanol und Polyole wie Diethylenglykol und Tetra- ethylenglykol, Kohlenwasserstoffe wie Petrolether, Benzol, Toluol, Xylol, Lactame wie Pyrrolidon oder Caprolactam oder alkylsubstituierte Lactame wie N-Methylpyrrolidon, N-Methylcapro- lactam oder N-Ethylcaprolactam sowie Carbonsäureester, vorzugs¬ weise von Carbonsäuren mit 1 bis 8 C-Atomen genannt. Auch Ammo¬ niak kann bei der Reaktion anwesend sein. Selbstverständlich können auch Mischungen organischer Lösungsmittel Anwendung finden. Mischungen aus Wasser und Alkanolen im Gewichtsverhältnis Wasser/Alkanol von 1 bis 75 zu 25 bis 99, vorzugsweise 1 bis 50 zu 50 bis 99 haben sich in einigen Fällen als besonders vorteil¬ haft herausgestellt.The aminocarbonitrile is advantageously in the form of a 1 to 50% by weight, in particular 5 to 50% by weight, particularly preferably 5 to 30% by weight solution in water (in which case the solvent is also the reactant) or used in water / solvent mixtures. Examples of solvents are alkanols such as methanol, ethanol, n- and i-propanol, n-, i- and t-butanol and polyols such as diethylene glycol and tetraethylene glycol, hydrocarbons such as petroleum ether, benzene, toluene, xylene, lactams such as pyrrolidone or caprolactam or alkyl-substituted lactams such as N-methylpyrrolidone, N-methylcaprolactam or N-ethylcaprolactam and carboxylic acid esters, preferably called carboxylic acids having 1 to 8 carbon atoms. Ammonia can also be present in the reaction. Mixtures of organic solvents can of course also be used. Mixtures of water and alkanols in a water / alkanol weight ratio of 1 to 75 to 25 to 99, preferably 1 to 50 50 to 99 have proven to be particularly advantageous in some cases.
Das erfindungsgemäße Verfahren führt man in Gegenwart von Titan- dioxid-Katalysatoren aus, die einen Rutil-Gehalt im Bereich von 0,1 bis 95, bevorzugt von 1 bis 90 Gew.-% und einen Anatas-Gehalt im Bereich von 99,9 bis 5, bevorzugt von 99 bis 10 Gew.-%, je¬ weils bezogen auf den Gesamtgehalt an Titandioxid, aufweisen.The process according to the invention is carried out in the presence of titanium dioxide catalysts which have a rutile content in the range from 0.1 to 95, preferably from 1 to 90% by weight and an anatase content in the range from 99.9 to 5, preferably from 99 to 10 wt .-%, each based on the total content of titanium dioxide.
In einer bevorzugten Ausführungsform führt man die Umsetzung in einem Festbett durch, wobei die Katalysatoren in Form von Strän¬ gen oder Tabletten eingesetzt werden, bevorzugt weisen dabei die Tabletten und Stränge einen Durchmesser zwischen 1 und 10 mm auf.In a preferred embodiment, the reaction is carried out in a fixed bed, the catalysts being used in the form of strands or tablets, the tablets and strands preferably having a diameter between 1 and 10 mm.
Zur Herstellung der Stränge und Tabletten, die man nach üblichen Methoden herstellen kann, verwendet man Titandioxid-Pulver, das bereits den gewünschten Gehalt an Anatas und Rutil aufweist oder das man durch Pyrolyse entweder ausgehend von einer reinen Ana- tas-Modifikation oder einer Mischform enthaltend Anatas- und Ru- til-Phasen oder einer Mischung von reinen Anatas- und Rutil-Modi¬ fikationen erhält, indem man bei entsprechender Temperatur und Verweilzeit (beides ist dem Fachmann bekannt, beispielsweise aus Catalysis Today 14, (1992) 225 - 242) solange pyrolysiert, bis das gewünschte Anatas-zu-Rutil-Verhältnis erreicht ist.To produce the strands and tablets, which can be produced by customary methods, titanium dioxide powder which already has the desired content of anatase and rutile or which is obtained by pyrolysis either starting from a pure anatase modification or a mixed form is used Anatase and rutile phases or a mixture of pure anatase and rutile modifications are obtained by using the appropriate temperature and residence time (both are known to the person skilled in the art, for example from Catalysis Today 14, (1992) 225-242). pyrolyzed until the desired anatase to rutile ratio is reached.
Entsprechende Pulver sind auf dem Markt erhältlich, beispiels¬ weise die Titandioxid-Pulver P25® (20 bis 30 Gew.-% Rutil und 80 bis 70 Gew.-% Anatas) von Degussa sowie S150® und S140® (jeweils 100 Gew.-% Anatas) von Finti-Kemira.Corresponding powders are available on the market, for example the titanium dioxide powders P25® (20 to 30% by weight of rutile and 80 to 70% by weight of anatase) from Degussa as well as S150® and S140® (each 100% by weight). % Anatas) by Finti-Kemira.
Das Titandioxid kann als solches oder als Trägerkatalysator, wo¬ bei es auf einen mechanisch und chemisch stabilen Träger meist mit hoher Oberfläche aufgebracht werden kann, verwendet werden.The titanium dioxide can be used as such or as a supported catalyst, whereby it can usually be applied to a mechanically and chemically stable support, usually with a high surface area.
Das Titandioxid kann durch Fällung aus wäßrigen Lösungen herge¬ stellt worden sein, z.B. nach dem Sulfatprozeß oder durch andere Verfahren wie die pyrogene Herstellung von feinen Titandioxid- Pulvern, die käuflich zu erhalten sind.The titanium dioxide can have been produced by precipitation from aqueous solutions, e.g. after the sulfate process or by other methods such as the pyrogenic production of fine titanium dioxide powders, which are commercially available.
Gewünschtenfalls kann man das Rutil-/Anatas-haltige Titandioxid mit anderen Oxiden wie Aluminiumoxid, Zirkonoxid oder Ceroxid abmischen. Zur Herstellung von Gemischen der verschiedenen Oxide stehen mehrere Methoden zur Wahl. Die Oxide oder deren Vorläufer¬ verbindungen, die durch Calzinieren in die Oxide umwandelbar sind, können z.B. durch eine gemeinsame Fällung aus Lösung herge¬ stellt werden. Dabei wird im allgemeinen eine sehr gute Ver¬ teilung der beiden verwendeten Oxide erhalten. Die Oxid- oder Vorläufergemische können auch durch eine Fällung des einen Oxids oder Vorläufers in Gegenwart des als Suspension von fein verteil¬ ten Teilchen vorliegenden zweiten Oxids oder Vorläufers ausge¬ fällt werden. Eine weitere Methode besteht im mechanischen Mi- sehen der Oxid- oder Vorlauferpulver, wobei dieses Gemisch als Ausgangsmaterial zur Herstellung von Strängen oder Tabletten Ver¬ wendung finden kann.If desired, the rutile / anatase-containing titanium dioxide can be mixed with other oxides such as aluminum oxide, zirconium oxide or cerium oxide. Several methods are available for producing mixtures of the different oxides. The oxides or their precursor compounds, which can be converted into the oxides by calcining, can be prepared from solution, for example, by co-precipitation. In general, a very good distribution of the two oxides used is obtained. The oxide or Precursor mixtures can also be precipitated by precipitation of one oxide or precursor in the presence of the second oxide or precursor, which is present as a suspension of finely divided particles. Another method consists in mechanical mixing of the oxide or precursor powder, this mixture being able to be used as a starting material for the production of strands or tablets.
Zur Herstellung von Trägerkatalysatoren bieten sich verschiedene Methoden an. So kann man das Titandioxid in Form eines Sols durch einfaches Tränken auf den Träger aufbringen. Durch Trocknen und Calzinieren werden die flüchtigen Bestandteile des Sols üblicher¬ weise aus dem Katalysator entfernt. Solche Sole sind für Titan¬ dioxid käuflich erhältlich.Various methods are available for producing supported catalysts. So you can apply the titanium dioxide in the form of a sol by simply soaking on the carrier. The volatile constituents of the sol are usually removed from the catalyst by drying and calcining. Such brines are commercially available for titanium dioxide.
Eine weitere Möglichkeit zum Aufbringen von Schichten des aktiven Titandioxids besteht in der Hydrolyse oder Pyrolyse von organi¬ schen oder anorganischen Verbindungen. So kann ein keramischer Träger mit Titandioxid durch Hydrolyse von Titan-Isopropylat oder anderen Ti-Alkoxiden in dünner Schicht belegt werden. Eine wei¬ tere geeignete Verbindung ist TiCl . Geeignete Träger sind Pulver, Stränge oder Tabletten des Titandioxids selbst oder anderer sta¬ biler Oxide wie Siliciumdioxid. Die verwendeten Träger können zur Verbesserung des Stofftransports makroporös ausgestaltet sein. Wichtig ist, daß man bei der Pyrolyse des Titandioxids darauf achtet, daß sowohl Rutil- als auch Anatasphasen in den obenge¬ nannten Bereichen entstehen.Another possibility for applying layers of the active titanium dioxide is the hydrolysis or pyrolysis of organic or inorganic compounds. For example, a ceramic support can be coated with titanium dioxide in a thin layer by hydrolysis of titanium isopropylate or other Ti alkoxides. Another suitable compound is TiCl. Suitable carriers are powders, extrudates or tablets of titanium dioxide itself or other stable oxides such as silicon dioxide. The carriers used can be designed to be macroporous in order to improve the mass transport. It is important that care is taken in the pyrolysis of the titanium dioxide that both rutile and anatase phases occur in the above-mentioned areas.
Nach dem erfindungsgemäßen Verfahren erhält man cyclische Lactame, insbesondere Caprolactam in hoher Ausbeute bei guten Selektivitäten und guter Konstanz der Katalysatoraktivität.The process according to the invention gives cyclic lactams, in particular caprolactam, in high yield with good selectivities and good constancy of the catalyst activity.
BeispieleExamples
Beispiele 1 bis 7Examples 1 to 7
In einen geheizten Rohrreaktor von 25 ml Inhalt (Durchmesser 6 mm; Länge 800 mm), der mit Titandioxid in Form von Tabletten oder Strängen gefüllt war, wurde bei 100 bar eine Lösung von 6-Aminocapronsäurenitril (ACN) in Wasser und Ethanol in den in der Tabelle angegebenen Gewichtsverhältnissen geleitet. Der den Reaktor verlassende Produktstrom wurde gaschromatographisch ana¬ lysiert. Die Ergebnisse sind ebenfalls der Tabelle zu entnehmen. Tabelle
Figure imgf000008_0001
A solution of 6-aminocapronitrile (ACN) in water and ethanol was introduced into the in a heated tubular reactor of 25 ml (diameter 6 mm; length 800 mm) filled with titanium dioxide in the form of tablets or strands at 100 bar weight ratios given in the table. The product stream leaving the reactor was analyzed by gas chromatography. The results are also shown in the table. table
Figure imgf000008_0001
Bsp. Katalysator Form Sulfat-Gehalt Rutil Anatas BET A U S [%] [%] [m /g]Example catalyst form sulfate content rutile anatase BET A U S [%] [%] [m / g]
1 P25 3 mm Strang 0,01 93 7 15 92 95 971 P25 3 mm strand 0.01 93 7 15 92 95 97
2 P25/DT511 3 mm Strang 0,5 18 82 41 90 98 932 P25 / DT51 1 3 mm strand 0.5 18 82 41 90 98 93
3 P25/S1502 3 mm Strang 0,06 16 84 50 89 97 923 P25 / S150 2 3 mm strand 0.06 16 84 50 89 97 92
4 P25 1, 5 mm Strang n.b. 20 80 48 91 99 93 zum Vergleich4 P25 1.5 mm strand n.a. 20 80 48 91 99 93 for comparison
5 VKR611®3 1, 5 mm Strang n.b. 100 0 5 5 10 535 VKR611® 3 1, 5 mm strand nb 100 0 5 5 10 53
6 DT51 4 mm Strang n.b. 0 100 36 78 90 856 DT51 4 mm strand n.a. 0 100 36 78 90 85
7 S150 3 mm Strang 0,17 0 100 108 90 99 917 S150 3 mm strand 0.17 0 100 108 90 99 91
1 Mischung aus 2/3 Gew.-Teilen P25®-Pulver, Rest DT51® (Rhδne-Poulenc) 1 mixture of 2/3 parts by weight of P25® powder, remainder DT51® (Rhδne-Poulenc)
2 Mischung aus 2/3 Gew.-Teilen P25®-Pulver, Rest S150® (Finti-Kemira) 2 mixture of 2/3 parts by weight of P25® powder, balance S150® (Finti-Kemira)
3 Rutil von Fa. Sachtleben, behandelt durch 2h Tempern bei 875°C n.b.= nicht bestimmt 3 Rutile from Sachtleben, treated by annealing for 2 hours at 875 ° C nb = not determined
A= Ausbeute; S = Selektivität; U = Umsatz BET= Oberfläche nach BET gemäß DIN 66 131 A = yield; S = selectivity; U = conversion BET = surface according to BET according to DIN 66 131

Claims

Patentansprüche claims
1. Verfahren zur Herstellung cyclischer Lactame durch Umsetzung von Aminocarbonsäurenitrilen mit Wasser in Gegenwart von1. Process for the preparation of cyclic lactams by reacting aminocarbonitriles with water in the presence of
Katalysatoren, dadurch gekennzeichnet, daß man die Umsetzung in flüssiger Phase in Gegenwart heterogener Katalysatoren auf der Basis von Titandioxid mit einem Rutil-Gehalt im Bereich von 0,1 bis 95 Gew.-% und einem Anatas-Gehalt im Bereich von 99,9 bis 5 Gew.-%, jeweils bezogen auf den Gesamtgehalt an Titandioxid, durchführt.Catalysts, characterized in that the reaction in the liquid phase in the presence of heterogeneous catalysts based on titanium dioxide with a rutile content in the range from 0.1 to 95% by weight and an anatase content in the range from 99.9 to 5 wt .-%, based in each case on the total content of titanium dioxide.
2. Verfahren nach Anspruch 1, dadurch gekennzeichnet, daß man die Umsetzung bei einer Temperatur im Bereich von 140 bis 320°C durchführt.2. The method according to claim 1, characterized in that one carries out the reaction at a temperature in the range of 140 to 320 ° C.
3. Verfahren nach einem der Ansprüche 1 bis 2, dadurch gekenn¬ zeichnet, daß man Aminocarbonsäurenitrile der Formel3. The method according to any one of claims 1 to 2, characterized gekenn¬ characterized in that aminocarbonitriles of the formula
H2N—(CH2)Itr—C---≡NH 2 N— (CH 2 ) Itr —C --- ≡N
wobeiin which
m 3, 4, 5 oder 6 ist, einsetzt.m is 3, 4, 5 or 6.
4. Verfahren nach Anspruch 3, dadurch gekennzeichnet, daß man als Aminocarbonsäurenitril 6-Aminocapronsäurenitril einsetzt4. The method according to claim 3, characterized in that 6-aminocapronitrile is used as the aminocarbonitrile
5. Verfahren nach einem der Ansprüche 1 bis 4, dadurch gekenn- zeichnet, daß man eine 1 bis 50 gew.-%ige Lösung des Amino- carbonsäurenitrils in Wasser oder in Wasser/org. Lösungs¬ mittel-Gemischen einsetzt. 5. The method according to any one of claims 1 to 4, characterized in that a 1 to 50 wt .-% solution of the aminocarbonitrile in water or in water / org. Solvent mixtures used.
PCT/EP1996/001891 1995-05-18 1996-05-07 Titanium dioxide-catalysed cyclisation in the liquid phase of 6-amino caproic acid nitrile to caprolactam WO1996036600A1 (en)

Priority Applications (12)

Application Number Priority Date Filing Date Title
HU9801131A HU220356B (en) 1995-05-18 1996-05-07 Titanium dioxide-catalysed cyclisation in the liquid phase of 6-amino-caproic acid nitrile to caprolactam
AU58147/96A AU700098B2 (en) 1995-05-18 1996-05-07 The preperation of caprolactam
BR9608470A BR9608470A (en) 1995-05-18 1996-05-07 Process to prepare lactamos cycles
MX9708676A MX9708676A (en) 1995-05-18 1996-05-07 Titanium dioxide-catalysed cyclisation in the liquid phase of 6-amino caproic acid nitrile to caprolactam.
NZ308485A NZ308485A (en) 1995-05-18 1996-05-07 Titanium dioxide-catalysed cyclisation in the liquid phase of 6-amino caproic acid nitrile to caprolactam
SK1548-97A SK154897A3 (en) 1995-05-18 1996-05-07 Method for the preparation of cyclic lactams
EA199700402A EA199700402A1 (en) 1995-05-18 1996-05-07 CATALYTIC CYCLICATION OF TITANIUM DIOXIDE IN THE LIQUID PHASE OF NITRIL 6-AMINOCAPRONIC ACID IN CAPROLACT
PL96323389A PL323389A1 (en) 1995-05-18 1996-05-07 Caprolaktam producing method
EP96919687A EP0815077A1 (en) 1995-05-18 1996-05-07 Titanium dioxide-catalysed cyclisation in the liquid phase of 6-amino caproic acid nitrile to caprolactam
JP8534516A JPH11505230A (en) 1995-05-18 1996-05-07 Method for producing caprolactam
BG102027A BG102027A (en) 1995-05-18 1997-11-06 Method of liquid phase cyclization catalyzed with titanium dioxide of nitrile of 6-aminocapronic acid to caprolactam
NO975268A NO307964B1 (en) 1995-05-18 1997-11-17 Titanium dioxide catalyzed liquid phase cycling of 6-aminocaproic acid nitrile to caprolactam

Applications Claiming Priority (2)

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DE19517821.1 1995-05-18
DE19517821A DE19517821A1 (en) 1995-05-18 1995-05-18 Process for the production of caprolactam

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DE19738464A1 (en) * 1997-09-03 1999-03-04 Basf Ag Use of moldings as a catalyst for the production of caprolactam
DE19738463C2 (en) * 1997-09-03 1999-09-23 Basf Ag Process for the production of caprolactam
CN101890370B (en) * 2010-08-05 2012-05-30 上海交通大学 Nano-titanium dioxide and polyphosphazene based composite optical catalyst and preparation method thereof

Citations (6)

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Publication number Priority date Publication date Assignee Title
US2301964A (en) * 1941-09-12 1942-11-17 Du Pont Method of preparing lactams
FR2029540A1 (en) * 1969-01-28 1970-10-23 Asahi Chemical Ind Epsilon caprolactam by one step synthesis
US4625023A (en) * 1985-09-03 1986-11-25 Allied Corporation Selective conversion of aliphatic and aromatic aminonitriles and/or dinitriles into lactams
US4628085A (en) * 1985-09-03 1986-12-09 Allied Corporation Use of silica catalyst for selective production of lactams
JPH0415766A (en) * 1990-05-01 1992-01-21 Meidensha Corp Gradation image processor
DE4339648A1 (en) * 1993-11-20 1995-05-24 Basf Ag Process for the production of caprolactam

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Publication number Priority date Publication date Assignee Title
US2029540A (en) * 1935-10-01 1936-02-04 Porteous William Trailer

Patent Citations (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US2301964A (en) * 1941-09-12 1942-11-17 Du Pont Method of preparing lactams
FR2029540A1 (en) * 1969-01-28 1970-10-23 Asahi Chemical Ind Epsilon caprolactam by one step synthesis
US4625023A (en) * 1985-09-03 1986-11-25 Allied Corporation Selective conversion of aliphatic and aromatic aminonitriles and/or dinitriles into lactams
US4628085A (en) * 1985-09-03 1986-12-09 Allied Corporation Use of silica catalyst for selective production of lactams
JPH0415766A (en) * 1990-05-01 1992-01-21 Meidensha Corp Gradation image processor
DE4339648A1 (en) * 1993-11-20 1995-05-24 Basf Ag Process for the production of caprolactam

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Title
CHEMICAL ABSTRACTS, vol. 71, no. 19, 10 November 1969, Columbus, Ohio, US; abstract no. 90878, FUKADA, TOSHIO ET AL: ".omega.-Aminoalkanenitriles" XP002009482 *

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