WO2004037785A1 - Method of obtaining dodecalactam using solid catalysts - Google Patents

Method of obtaining dodecalactam using solid catalysts Download PDF

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Publication number
WO2004037785A1
WO2004037785A1 PCT/ES2003/000543 ES0300543W WO2004037785A1 WO 2004037785 A1 WO2004037785 A1 WO 2004037785A1 ES 0300543 W ES0300543 W ES 0300543W WO 2004037785 A1 WO2004037785 A1 WO 2004037785A1
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process according
carried out
solvent
nanolaminar
silicate
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PCT/ES2003/000543
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Spanish (es)
French (fr)
Inventor
Avelino CORMA CANÓS
Sara Iborra Chornet
Marie-Isabelle RODRÍGUEZ
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Consejo Superior De Investigaciones Científicas
Universidad Politécnica De Valencia
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Priority to AU2003274159A priority Critical patent/AU2003274159A1/en
Publication of WO2004037785A1 publication Critical patent/WO2004037785A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
    • B01J29/7038—MWW-type, e.g. MCM-22, ERB-1, ITQ-1, PSH-3 or SSZ-25
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J29/00—Catalysts comprising molecular sieves
    • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
    • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07D—HETEROCYCLIC COMPOUNDS
    • C07D201/00—Preparation, separation, purification or stabilisation of unsubstituted lactams
    • C07D201/02—Preparation of lactams
    • C07D201/04—Preparation of lactams from or via oximes by Beckmann rearrangement
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
    • B01J2229/10—After treatment, characterised by the effect to be obtained
    • B01J2229/16—After treatment, characterised by the effect to be obtained to increase the Si/Al ratio; Dealumination

Definitions

  • the present invention relates to the preparation of dodecalactam (2-azacyclotridecanone), the precursor of the Nylon-12 monomer, and particularly to the use of laminar materials as acid catalysts for the production of Beckmann transposition of the oxime of Beckmann oxime of cyclododecanone
  • Zeolites such as Beta and MF have been used successfully in the process of transposition of the oxime of the Cyclohexanone, however, these types of materials may have limitations in the transposition of oximes of larger molecular size, such as the cyclododecanone oxime.
  • solid nanolaminar solids such as ITQ-2 (Corma A. et al. O97 / 7290 (1997), ITQ-6 (Corma A. et al. J. Am. Chem. Soc.
  • the present invention relates to the use of acid delaminated solid materials that we call nanolaminar, prepared by the delamination of a precursor zeolite with laminar structure.
  • This delamination process results in a new nanolaminar material that has a high external surface area (> 500 m / g) and whose catalytic centers are highly accessible to large molecules and that facilitate rapid desorption of reaction products.
  • the present invention relates to a process for the preparation of dodecalactam, characterized in that it comprises contacting the oxime of the cyclododecanone with an acidic nanola silicate having an 1 IV / ⁇ ⁇ 11 ratio between 15 and 50, wherein T IV represents one or more tetravalent cations other than silicon and T 111 represents one or more trivalent cations.
  • the present invention relates to a process for the preparation of dodecalactam, characterized in that it comprises contacting the oxime of the cyclododecanone with an acidic nanolaminar silicate having a T ⁇ / T 111 ratio between 15 and 50, wherein T IV represents one or more tetravalent cations other than silicon and T IIX represents one or more trivalent cations.
  • delaminated materials are preferably silicates prepared according to the process described in the references cited above.
  • T IV represents one or more tetravalent cations other than silicon, selected from Ge,
  • T 111 represents one or more trivalent cations selected from Al, B, Fe, Ga and mixtures thereof.
  • the nanolaminar silicate has a surface area of 500 m 2 / g or greater.
  • the nanolaminar silicate is one of the following types: of the ITQ-2 type, of the ITQ-6 type, of the type
  • ITQ-18 of the type ITQ-20.
  • the reaction can be carried out in the gas phase or in the liquid phase.
  • the reactor may be a reactor selected from a continuous stirred tank reactor, a stationary fixed bed reactor, a fluidized mobile bed discontinuous reactor, and a riser type reactor.
  • the process is preferably carried out in the presence of a solvent, at a pressure of less than 20 x 10 5 Pa (20 bar) and at a temperature between 40 and 350 ° C. More preferably, the liquid phase process is carried out at a temperature between 100 and 300 ° C.
  • an example of a solvent is a solvent selected from an aromatic hydrocarbon, a halogenated aromatic hydrocarbon, a dialkylsulfoxide, an N, N-dialkylamide, an alcohol, and a sulfolane.
  • a preferred solvent is one selected from benzene and toluene.
  • a preferred solvent is one selected from chlorobenzene and dichlorobenzene.
  • Other possible solvents for the liquid phase process are, for example, dialkylsulfoxides, such as dimethylsulfoxide and diethyl sulfoxide, or N, N-dialkylamides, such as dimethylformamide and diethylformamide.
  • the group of preferred solvents are aromatic hydrocarbons (benzene and toluene) and alcohols such as methanol, butanol, pentanol, and hexanol.
  • a nitrile can be used as a solvent both in the liquid phase and in the gas phase.
  • Said nitrile can be both aromatic and aliphatic.
  • An especially preferred example of nitrile is one selected from benzonitrile, adiponitrile and 3-methoxy-propanonitrile
  • said acidic nanolaminar solids are for example ITQ-2, ITQ-6, ITQ-18, and ITQ-20 and the process is preferably carried out in the gas phase or in the liquid phase, at moderate temperatures.
  • the process of the present invention provides a much higher yield to lactam than is obtained with crystalline aluminosilicates such as Beta zeolites or with mesoporous molecular sieves (MCM-41).
  • the amount of catalyst is preferably in a weight ratio with respect to the oxime between 0.1: 1 and 6: 1, preferably between 0.5: 1 and 3: 1.
  • a stirred tank batch reactor and an oxime catalyst ratio between 0.1: 1 and 6: 1, preferably between 0.5: 1 and 3: 1, are used.
  • the catalyst can be regenerated after use by washing with a solvent and / or by calcining at temperatures between 450 and 500 ° C.
  • the catalyst in a weight ratio with respect to the cyclododecanone oxime of 2: 1, is activated by heating at 300 ° C under a pressure of 133.21 Pa (1 Tor) for 2h.
  • the catalyst is added to a solution of oxime (lg) in chlorobenzene (200 ml).
  • the resulting suspension is heated at a temperature of 130 ° C at atmospheric pressure for 3 hours in a batch reactor under stirring.
  • the solvent is then distilled under vacuum and the crude is analyzed by gas chromatography.
  • the molar yield in dodecalactam is 98% with a selectivity of 100%.
  • the catalyst in a weight ratio with respect to the cyclododecanone oxime of 1: 1, is activated by heating at 300 ° C under a pressure of 133.21 Pa (1 Tor) for 2h.
  • the catalyst is added to a solution of oxime (lg) in chlorobenzene (200 ml).
  • the resulting suspension is heated at a temperature of 130 ° C at atmospheric pressure for 10 hours in a batch reactor under stirring.
  • the solvent is evaporated by vacuum distillation and the crude is analyzed by gas chromatography.
  • the molar yield in dodecalactam is 65% with a selectivity of 100%.
  • the catalyst in a weight ratio with respect to the cyclododecanone oxime of 1: 1 is activated by heating at 300 ° C under a pressure of 133.21 Pa (1 Tor) for 2h.
  • the catalyst is added to a solution of oxime (lg) in sulfolane (200 ml).
  • the resulting suspension is heated at a temperature of 130 ° C at atmospheric pressure for 3 hours in a batch reactor under stirring.
  • the solvent is evaporated by vacuum distillation and the crude is analyzed by gas chromatography.
  • the molar yield in dodecalactam is 80% with a selectivity of 100%.
  • the catalyst in a weight ratio with respect to the cyclododecanone oxime of 2: 1, is activated by heating at 300 ° C under a pressure of 133.21 Pa (1 Tor) for 2h.
  • the catalyst is added to a solution of oxime (lg) in chlorobenzene (200 ml).
  • the resulting suspension is heated at a temperature of 130 ° C at atmospheric pressure for 3 hours in a batch reactor under stirring.
  • the solvent is vacuum distillate and the crude is analyzed by gas chromatography.
  • the molar yield in dodecalactam is 49% with a selectivity of 100%.
  • the catalyst in a weight ratio with respect to the cyclododecanone oxime of 2: 1, is activated by heating at 300 ° C under a pressure of 133.21 Pa (1 Tor) for 2h.
  • the catalyst is added to a solution of oxime (lg) in chlorobenzene (200 ml).
  • the resulting suspension is heated at a temperature of 130 ° C at atmospheric pressure for 3 hours in a batch reactor under stirring.
  • the solvent is then distilled under vacuum and the crude is analyzed by gas chromatography.
  • the molar yield in dodecalactam is 75% with a selectivity of 100%. Table 1 summarizes and compares the results of examples 1, 4 and 5.
  • the catalyst in a weight ratio with respect to the cyclododecanone oxime of 2: 1, is activated by heating at 300 ° C under a pressure of 133.21 Pa (1 Tor) for 2h.
  • the catalyst is added to a solution of oxime (lg) in benzonitrile (200 mL).
  • the resulting suspension is heated at a temperature of 130 ° C at atmospheric pressure for 5 hours in a batch reactor under stirring.
  • the solvent is evaporated by vacuum distillation and the crude is analyzed by gas chromatography.
  • the molar yield in dodecalactam is 95% with a selectivity of 100%.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Catalysts (AREA)

Abstract

The invention relates to a method of preparing dodecalactam, the precursor of the monomer for Nylon-12, and, in particular, to a method involving the use of laminar materials as heterogeneous acid catalysts for the production of dodecalactam by means of Beckmann transposition of the cyclododecanone oxime.

Description

TítuloTitle
Procedimiento de obtención de dodecalactama mediante el uso de catalizadores sólidosProcedure for obtaining dodecalactam through the use of solid catalysts
Campo de la TécnicaTechnical Field
Preparación de dodecalactama por transposición de Beckmann de la oxima de la dodecanona.Preparation of dodecalactam by Beckmann transposition of the dodecanone oxime.
Antecedentes La presente invención se refiere a la preparación de dodecalactama (2-azaciclotridecanona) , el precursor del monómero del Nylon-12, y particularmente a la utilización de materiales laminares como catalizadores ácidos para la producción de dodecalactama por transposición de Beckmann de la oxima de la ciclododecanona .BACKGROUND The present invention relates to the preparation of dodecalactam (2-azacyclotridecanone), the precursor of the Nylon-12 monomer, and particularly to the use of laminar materials as acid catalysts for the production of Beckmann transposition of the oxime of Beckmann oxime of cyclododecanone
El proceso de transposición de una oxima en su amida utilizando ácido sulfúrico concentrado como catalizador, conocido como transposición de Beckmann, es un proceso comúnmente usado para la preparación de lactamas, en particular la ε-caprolactama . Sin embargo este proceso presenta importantes desventajas tales como la necesidad de utilizar grandes cantidades de sulfúrico concentrado, la producción de grandes cantidades de sales (sulfato amónico) como subproducto, problemas de corrosión en aparatos etc. Para evitar todos estos inconvenientes, la utilización de catalizadores sólidos ácidos, especialmente aquellos basados en zeolitas sintéticas se ha presentado como una de las alternativas más prometedoras para llevar a cabo este tipo de procesos. Entre ellas zeolitas tipo Faujasita (Landis, P.S. et al., ". Catal . 6, 245 (1996); Aucejo, A. et al., Appl . Catal . 22, 187 (1986); Corma, A. et al. Zeoli tes 11, 593 (1991), Beta(Dai, LX. , et al., Chem. Commun . 1071 (1996); Corma, A., et al. ". Catal . 177, 267 (1998)), Pentasil (1. Róseler, J. , et al. Appl . Catal . 144, 319 (1996); Kitamura M. et al., EP-1028108 (2000); Sato H. EP-0234088 (1996); Takahashi , T. , et al., J. Chem. Eng. 69, 1096 (1991)), Mordenita (Sato, H. , et al. Stud. Surf. Sci . Catal . 28, 755) y tamices moleculares mesoporosos (MCM-41) ( Dai, L.X.,et al., Catal . Lett . 53, 211 (1998)) han sido utilizados como catalizadores en la transposición de Beckmann de la ciclohexanona oxima tanto en fase liquida como gaseosa. El proceso en fase gas requiere la utilización de elevadas temperaturas, entre 300 y 450 °C con objeto de mantener la oxima y los productos de reacción en fase gaseosa. Bajo estas condiciones, utilización de zeolitas tales como ZSM-5, ZSM-11, ZSM-23 o silicalitas (Kitamura M. et al., EP-1028108 (2000); Sato H., EP-0234088 (1986); Sato, H. et al., Chem Lett . 1987 (1993)) ha dado buenos resultados en el proceso de transposición de la oxima de la ciclohexanona. Sin embargo, la utilización de elevadas temperaturas también presenta importantes desventajas tales como la formación de subproductos que provocan la desactivación rápida del catalizador y la necesidad de utilización de procesos de purificación de la lactama extremadamente costosos. Por otra parte, la realización de este proceso en fase líquida y a temperaturas moderadas, puede ser una interesante alternativa si se utiliza tanto el catalizador como el disolvente más adecuado que permita una selectividad máxima a lactama, minimizando la adsorción de productos sobre la superficie del catalizador y por lo tanto el envenenamiento del mismo. La alternativa del proceso en fase líquida, es incluso más interesante para el caso de oximas de masa molecular superior al de la oxima de la ciclohexanona.The process of transposition of an oxime in its amide using concentrated sulfuric acid as a catalyst, known as Beckmann transposition, is a process commonly used for the preparation of lactams, in particular ε-caprolactam. However, this process has important disadvantages such as the need to use large amounts of concentrated sulfuric acid, the production of large quantities of salts (ammonium sulfate) as a byproduct, corrosion problems in devices, etc. To avoid all these inconveniences, the use of solid acid catalysts, especially those based on synthetic zeolites, has been presented as one of the most promising alternatives for carrying out this type of process. Among them Zeolites type Faujasita (Landis, PS et al., " . Catal. 6, 245 (1996); Aucejo, A. et al., Appl. Catal. 22, 187 (1986); Corma, A. et al. Zeoli tes 11, 593 (1991), Beta (Dai, LX., Et al., Chem. Commun. 1071 (1996); Corma, A., et al. " . Catal. 177, 267 (1998)), Pentasil (1. Róseler, J., et al. Appl. Catal. 144, 319 (1996); Kitamura M. et al., EP-1028108 (2000); Sato H. EP-0234088 (1996 ); Takahashi, T., et al., J. Chem. Eng. 69, 1096 (1991)), Mordenita (Sato, H., et al. Stud. Surf. Sci. Catal. 28, 755) and molecular sieves Mesoporous (MCM-41) (Dai, LX, et al., Catal. Lett. 53, 211 (1998)) have been used as catalysts in the Beckmann transposition of cyclohexanone oxime in both liquid and gas phase. The gas phase process requires the use of high temperatures, between 300 and 450 ° C in order to maintain the oxime and the gas phase reaction products. Under these conditions, use of zeolites such as ZSM-5, ZSM-11, ZSM-23 or silicalites (Kitamura M. et al., EP-1028108 (2000); Sato H., EP-0234088 (1986); Sato, H. et al., Chem Lett. 1987 (1993)) has given good results in the process of transposition of cyclohexanone oxime. However, the use of high temperatures also presents important disadvantages such as the formation of by-products that cause rapid catalyst deactivation and the need for extremely expensive lactation purification processes. On the other hand, the realization of this process in liquid phase and at moderate temperatures, can be an interesting alternative if both the catalyst and the most suitable solvent that allow a maximum selectivity to lactam are used, minimizing the adsorption of products on the surface of the catalyst and therefore the poisoning of it. The alternative of the liquid phase process is even more interesting in the case of oximes of molecular mass greater than that of the cyclohexanone oxime.
Zeolitas como Beta y MF han sido utilizadas con éxito en el proceso de transposición de la oxima de la ciclohexanona, sin embargo este tipo de materiales pueden presentar limitaciones en la transposición de oximas de mayor tamaño molecular tal como es el caso de la oxima de la ciclododecanona . La mayor parte de las patentes relacionadas con la transposición de la oxima de la ciclododecanona describen procesos realizados en fase líquida, a temperaturas moderadas y utilizando ácido sulfúrico como catalizador (DE-3538859, DE-2905680, ES-2048098, ES-2048099) , ácido clorhídrico (JP-09227509, WO-9901424, EP-798290) , ácido trifluoroacético (JP-51034185) o pentóxido de fosforo (EP- 1193251, Sumitomo) .Zeolites such as Beta and MF have been used successfully in the process of transposition of the oxime of the Cyclohexanone, however, these types of materials may have limitations in the transposition of oximes of larger molecular size, such as the cyclododecanone oxime. Most of the patents related to the transposition of cyclododecanone oxime describe processes carried out in the liquid phase, at moderate temperatures and using sulfuric acid as a catalyst (DE-3538859, DE-2905680, ES-2048098, ES-2048099), hydrochloric acid (JP-09227509, WO-9901424, EP-798290), trifluoroacetic acid (JP-51034185) or phosphorus pentoxide (EP-1193251, Sumitomo).
Por otra parte sólidos nanolaminares con carácter ácido tales como por ejemplo ITQ-2 (Corma A. et al. O97/7290 (1997), ITQ-6 (Corma A. et al. J. Am . Chem . Soc.On the other hand, solid nanolaminar solids such as ITQ-2 (Corma A. et al. O97 / 7290 (1997), ITQ-6 (Corma A. et al. J. Am. Chem. Soc.
122, 2804 (1999)), ITQ-18 (Corma A., et al., WO 20000707,122, 2804 (1999)), ITQ-18 (Corma A., et al., WO 20000707,
(2001)), e ITQ-20 (Corma A. et al., WO-0260816, (2002)) no han sido previamente divulgados como posibles catalizadores sólidos para la conversión de la oxima de dodecahexanona en dodecalactama en un procedimiento que supera los inconvenientes anteriormente mencionados del estado de la técnica .(2001)), and ITQ-20 (Corma A. et al., WO-0260816, (2002)) have not previously been disclosed as possible solid catalysts for the conversion of dodecahexanone oxime into dodecalactam in a procedure that exceeds previously mentioned drawbacks of the prior art.
La presente invención se refiere a la utilización de materiales sólidos deslaminados con carácter ácido que denominamos nanolaminares, preparados mediante la deslaminación de una zeolita precursora con estructura laminar. Este proceso de deslaminación da lugar a un nuevo material nanolaminar que posee una elevada área superficial externa (>500 m/g) y cuyos centros catalíticos son altamente accesibles a moléculas de gran tamaño y que facilitan una rápida desorción de los productos de reacción. Breve descripción de la InvenciónThe present invention relates to the use of acid delaminated solid materials that we call nanolaminar, prepared by the delamination of a precursor zeolite with laminar structure. This delamination process results in a new nanolaminar material that has a high external surface area (> 500 m / g) and whose catalytic centers are highly accessible to large molecules and that facilitate rapid desorption of reaction products. Brief Description of the Invention
La presente invención se refiere a un procedimiento para la preparación de dodecalactama, caracterizado porque comprende poner en contacto la oxima de la ciclododecanona con un silicato nanola inar con carácter ácido que posee una relación 1IV/ττ11 comprendida entre 15 y 50, en donde TIV representa uno o más cationes tetravalentes distintos de silicio y T111 representa uno o más cationes trivalentes.The present invention relates to a process for the preparation of dodecalactam, characterized in that it comprises contacting the oxime of the cyclododecanone with an acidic nanola silicate having an 1 IV / τ τ11 ratio between 15 and 50, wherein T IV represents one or more tetravalent cations other than silicon and T 111 represents one or more trivalent cations.
Descripción detallada de la InvenciónDetailed description of the invention
La presente invención se refiere a un procedimiento para la preparación de dodecalactama, caracterizado porque comprende poner en contacto la oxima de la ciclododecanona con un silicato nanolaminar con carácter ácido que posee una relación T^/T111 comprendida entre 15 y 50, en donde TIV representa uno o más cationes tetravalentes distintos de silicio y TIIX representa uno o más cationes trivalentes.The present invention relates to a process for the preparation of dodecalactam, characterized in that it comprises contacting the oxime of the cyclododecanone with an acidic nanolaminar silicate having a T ^ / T 111 ratio between 15 and 50, wherein T IV represents one or more tetravalent cations other than silicon and T IIX represents one or more trivalent cations.
Los materiales deslaminados (materiales nanolaminares) a los que se refiere la presente invención son preferentemente silicatos preparados según el proceso que se describe en las referencias citadas anteriormente.The delaminated materials (nanolaminar materials) referred to in the present invention are preferably silicates prepared according to the process described in the references cited above.
De manera preferida TIV representa uno o más cationes tetravalentes distinto de silicio, seleccionados entre Ge,Preferably, T IV represents one or more tetravalent cations other than silicon, selected from Ge,
Ti, Sn y mezclas de ellos. De manera preferida T111 representa uno o más cationes trivalentes seleccionados entre Al, B, Fe, Ga y mezclas de ellos .Ti, Sn and mixtures of them. Preferably T 111 represents one or more trivalent cations selected from Al, B, Fe, Ga and mixtures thereof.
Preferentemente el silicato nanolaminar posee un área superficial de 500 m2/g o superior. Preferentemente el silicato nanolaminar es uno de los tipos siguientes: del tipo ITQ-2, del tipo ITQ-6, del tipoPreferably, the nanolaminar silicate has a surface area of 500 m 2 / g or greater. Preferably, the nanolaminar silicate is one of the following types: of the ITQ-2 type, of the ITQ-6 type, of the type
ITQ-18, del tipo ITQ-20. La reacción se puede realizar en fase gas o en fase líquida.ITQ-18, of the type ITQ-20. The reaction can be carried out in the gas phase or in the liquid phase.
El reactor puede ser un reactor seleccionado entre un reactor continuo de tanque agitado, un reactor discontinuo de lecho fijo, un reactor discontinuo de lecho móvil fluidizado, y un reactor de tipo riser.The reactor may be a reactor selected from a continuous stirred tank reactor, a stationary fixed bed reactor, a fluidized mobile bed discontinuous reactor, and a riser type reactor.
En el caso de que se lleve a cabo el procedimiento en fase líquida, se realiza preferentemente en presencia de un disolvente, a una presión inferior a 20xl05 Pa (20 bares) y a una temperatura entre 40 y 350°C. De manera más preferida aún el procedimiento en fase líquida se realiza a una temperatura entre 100 y 300 °C.In the case where the process is carried out in the liquid phase, it is preferably carried out in the presence of a solvent, at a pressure of less than 20 x 10 5 Pa (20 bar) and at a temperature between 40 and 350 ° C. More preferably, the liquid phase process is carried out at a temperature between 100 and 300 ° C.
Cuando se realiza en fase líquida, un ejemplo de un disolvente es un disolvente seleccionado entre un hidrocarburo aromático, un hidrocarburo aromático halogenado, un dialquilsulfoxido, una N,N-dialquilamida, un alcohol, y un sulfolano.When performed in the liquid phase, an example of a solvent is a solvent selected from an aromatic hydrocarbon, a halogenated aromatic hydrocarbon, a dialkylsulfoxide, an N, N-dialkylamide, an alcohol, and a sulfolane.
En el caso de utilizar para la reacción en fase líquida un hidrocarburo aromático, un disolvente preferido es uno seleccionado entre benceno y tolueno. Cuando el procedimiento se lleva en fase líquida con un hidrocarburo aromático halogenado un disolvente preferido es uno seleccionado entre el clorobenceno y diclorobenceno . Otros disolventes posibles para el procedimiento en fase líquida son por ejemplo los dialquilsulfóxidos, como por ejemplo el dimetilsulfóxido y el dietilsulfóxido, o las N,N- dialquilamidas, tales como la dimetilformamida y la dietilformamida .In the case of using an aromatic hydrocarbon for the liquid phase reaction, a preferred solvent is one selected from benzene and toluene. When the process is carried out in liquid phase with a halogenated aromatic hydrocarbon, a preferred solvent is one selected from chlorobenzene and dichlorobenzene. Other possible solvents for the liquid phase process are, for example, dialkylsulfoxides, such as dimethylsulfoxide and diethyl sulfoxide, or N, N-dialkylamides, such as dimethylformamide and diethylformamide.
Cuando el procedimiento se lleva a cabo en fase gaseosa, el grupo de disolventes preferidos son hidrocarburos aromáticos (benceno y tolueno) y alcoholes tales como metanol, butanol, pentanol, y hexanol . Además, tanto en fase líquida como en fase gaseosa se puede utilizar como disolvente un nitrilo. Dicho nitrilo puede ser tanto aromático como alifático. Un ejemplo de nitrilo especialmente preferido es uno seleccionado entre benzonitrilo, adiponitrilo y 3-metoxi-propanonitriloWhen the process is carried out in the gas phase, the group of preferred solvents are aromatic hydrocarbons (benzene and toluene) and alcohols such as methanol, butanol, pentanol, and hexanol. In addition, a nitrile can be used as a solvent both in the liquid phase and in the gas phase. Said nitrile can be both aromatic and aliphatic. An especially preferred example of nitrile is one selected from benzonitrile, adiponitrile and 3-methoxy-propanonitrile
Preferentemente dichos sólidos nanolaminares con carácter ácido son por ejemplo ITQ-2, ITQ-6, ITQ-18, e ITQ- 20 y el procedimiento se lleva preferentemente a cabo en fase gas o en fase líquida, a temperaturas moderadas. El procedimiento de la presente invención proporciona un rendimiento muy superior a lactama del que se obtiene con aluminosilicatos cristalinos tales como las zeolitas Beta o con tamices moleculares mesoporosos (MCM-41) .Preferably said acidic nanolaminar solids are for example ITQ-2, ITQ-6, ITQ-18, and ITQ-20 and the process is preferably carried out in the gas phase or in the liquid phase, at moderate temperatures. The process of the present invention provides a much higher yield to lactam than is obtained with crystalline aluminosilicates such as Beta zeolites or with mesoporous molecular sieves (MCM-41).
La cantidad de catalizador se encuentra preferentemente en una proporción en peso respecto a la oxima entre 0.1:1 y 6:1, preferentemente entre 0.5:1 y 3:1.The amount of catalyst is preferably in a weight ratio with respect to the oxime between 0.1: 1 and 6: 1, preferably between 0.5: 1 and 3: 1.
En una realización preferida se utiliza un reactor discontinuo de tanque agitado y una proporción de catalizador a oxima entre 0.1:1 y 6:1, preferentemente entre 0.5:1 y 3:1.In a preferred embodiment, a stirred tank batch reactor and an oxime catalyst ratio between 0.1: 1 and 6: 1, preferably between 0.5: 1 and 3: 1, are used.
El catalizador se puede regenerar tras su uso mediante lavado con un disolvente y/o por calcinación a temperaturas entre 450 y 500 °C.The catalyst can be regenerated after use by washing with a solvent and / or by calcining at temperatures between 450 and 500 ° C.
Según el procedimiento de la presente invención se obtiene dodecalactama con alto rendimiento (98 %) y selectividad (100%) . EJEMPLOS Ejemplo 1According to the process of the present invention dodecalactam is obtained with high yield (98%) and selectivity (100%). EXAMPLES Example 1
En este ejemplo se describe la obtención de la dodecalactama a partir de la ciclododecanona oxima utilizando un silicato nanolaminar obtenido por deslaminación de un precursor laminar de zeolita MWW, y que se denomina ITQ-2 con una relación Si/Al = 50.This example describes the obtaining of dodecalactam from cyclododecanone oxime using a nanolaminar silicate obtained by delamination of a MWW zeolite laminar precursor, which is called ITQ-2 with a Si / Al ratio = 50.
Antes de su uso, el catalizador en una relación en peso con respecto a la oxima de la ciclododecanona de 2:1, se activa por calentamiento a 300 °C bajo una presión de 133,21 Pa (1 Tor) durante 2h. El catalizador se añade a una disolución de oxima (lg) en clorobenceno (200 mi) . La suspensión resultante se calienta a la temperatura de 130 °C a presión atmosférica durante 3h en un reactor discontinuo bajo agitación. A continuación el disolvente se destila a vacío y el crudo se analiza por cromatografía de gases. El rendimiento molar en dodecalactama es del 98 % con una selectividad del 100%.Before use, the catalyst in a weight ratio with respect to the cyclododecanone oxime of 2: 1, is activated by heating at 300 ° C under a pressure of 133.21 Pa (1 Tor) for 2h. The catalyst is added to a solution of oxime (lg) in chlorobenzene (200 ml). The resulting suspension is heated at a temperature of 130 ° C at atmospheric pressure for 3 hours in a batch reactor under stirring. The solvent is then distilled under vacuum and the crude is analyzed by gas chromatography. The molar yield in dodecalactam is 98% with a selectivity of 100%.
Ejemplo 2Example 2
En este ejemplo se describe la obtención de la dodecalactama a partir de la ciclododecanona oxima utilizando un silicato nanolaminar del tipo ITQ-2 (Si/Al =50) en una relación en peso con respecto a la oxima de 1:1.In this example, the preparation of dodecalactam from cyclododecanone oxime is described using a nanolaminar silicate of the ITQ-2 type (Si / Al = 50) in a weight ratio with respect to the 1: 1 oxime.
Antes de su uso, el catalizador en una relación en peso con respecto a la oxima de la ciclododecanona de 1:1, se activa por calentamiento a 300 °C bajo una presión de 133,21 Pa (1 Tor) durante 2h. El catalizador se añade a una disolución de oxima (lg) en clorobenceno (200 mi) . La suspensión resultante se calienta a la temperatura de 130 °C a presión atmosférica durante lOh en un reactor discontinuo bajo agitación. El disolvente se evapora por destilación a vacio y el crudo se analiza por cromatografía de gases. El rendimiento molar en dodecalactama es de 65 % con una selectividad del 100%.Before use, the catalyst in a weight ratio with respect to the cyclododecanone oxime of 1: 1, is activated by heating at 300 ° C under a pressure of 133.21 Pa (1 Tor) for 2h. The catalyst is added to a solution of oxime (lg) in chlorobenzene (200 ml). The resulting suspension is heated at a temperature of 130 ° C at atmospheric pressure for 10 hours in a batch reactor under stirring. The solvent is evaporated by vacuum distillation and the crude is analyzed by gas chromatography. The molar yield in dodecalactam is 65% with a selectivity of 100%.
Ej emplo 3Ex emplo 3
En este ejemplo se describe la obtención de la dodecalactama a partir de la ciclododecanona oxima utilizando un silicato nanolaminar del tipo ITQ-2 (Si/Al= 50) y se observa la influencia del disolvente al compararlo con el ejemplo 2. Antes de su uso, el catalizador en una relación en peso con respecto a la oxima de la ciclododecanona de 1:1, se activa por calentamiento a 300 °C bajo una presión de 133,21 Pa (1 Tor) durante 2h. El catalizador se añade a una disolución de oxima (lg) en sulfolano (200 mi) . La suspensión resultante se calienta a la temperatura de 130 °C a presión atmosférica durante 3h en un reactor discontinuo bajo agitación. El disolvente se evapora por destilación a vacío y el crudo se analiza por cromatografía de gases. El rendimiento molar en dodecalactama es del 80 % con una selectividad del 100%.This example describes how to obtain dodecalactam from cyclododecanone oxime using a nanolaminar silicate of the type ITQ-2 (Si / Al = 50) and the influence of the solvent is observed when compared with example 2. Before use , the catalyst in a weight ratio with respect to the cyclododecanone oxime of 1: 1, is activated by heating at 300 ° C under a pressure of 133.21 Pa (1 Tor) for 2h. The catalyst is added to a solution of oxime (lg) in sulfolane (200 ml). The resulting suspension is heated at a temperature of 130 ° C at atmospheric pressure for 3 hours in a batch reactor under stirring. The solvent is evaporated by vacuum distillation and the crude is analyzed by gas chromatography. The molar yield in dodecalactam is 80% with a selectivity of 100%.
Ejemplo 4Example 4
A modo comparativo se describe en este ejemplo los resultados obtenidos con una zeolita acida de poro grande (Beta), con una relación Si/Al = 50.By way of comparison, the results obtained with a large pore zeolite acid (Beta), with a Si / Al ratio = 50, are described in this example.
Antes de su uso, el catalizador en una relación en peso con respecto a la oxima de la ciclododecanona de 2:1, se activa por calentamiento a 300 °C bajo una presión de 133,21 Pa (1 Tor) durante 2h. El catalizador se añade a una disolución de oxima (lg) en clorobenceno (200 mi) . La suspensión resultante se calienta a la temperatura de 130 °C a presión atmosférica durante 3h en un reactor discontinuo bajo agitación. A continuación el disolvente se destila a vacío y el crudo se analiza por cromatografía de gases. El rendimiento molar en dodecalactama es del 49 % con una selectividad del 100%.Before use, the catalyst in a weight ratio with respect to the cyclododecanone oxime of 2: 1, is activated by heating at 300 ° C under a pressure of 133.21 Pa (1 Tor) for 2h. The catalyst is added to a solution of oxime (lg) in chlorobenzene (200 ml). The resulting suspension is heated at a temperature of 130 ° C at atmospheric pressure for 3 hours in a batch reactor under stirring. Then the solvent is vacuum distillate and the crude is analyzed by gas chromatography. The molar yield in dodecalactam is 49% with a selectivity of 100%.
Ej emplo 5Ex emplo 5
A modo comparativo se describe en este ejemplo los resultados obtenidos con un tamiz molecular mesoporoso CM- 41, con una relación Si/Al = 50.By way of comparison, the results obtained with a CM-41 mesoporous molecular sieve, with a Si / Al ratio = 50, are described in this example.
Antes de su uso, el catalizador en una relación en peso con respecto a la oxima de la ciclododecanona de 2:1, se activa por calentamiento a 300 °C bajo una presión de 133,21 Pa (1 Tor) durante 2h. El catalizador se añade a una disolución de oxima (lg) en clorobenceno (200 mi) . La suspensión resultante se calienta a la temperatura de 130 °C a presión atmosférica durante 3h en un reactor discontinuo bajo agitación. A continuación el disolvente se destila a vacío y el crudo se analiza por cromatografía de gases. El rendimiento molar en dodecalactama es del 75 % con una selectividad del 100%. En Tabla 1 se resumen y comparan los resultados de los ejemplos 1, 4 y 5.Before use, the catalyst in a weight ratio with respect to the cyclododecanone oxime of 2: 1, is activated by heating at 300 ° C under a pressure of 133.21 Pa (1 Tor) for 2h. The catalyst is added to a solution of oxime (lg) in chlorobenzene (200 ml). The resulting suspension is heated at a temperature of 130 ° C at atmospheric pressure for 3 hours in a batch reactor under stirring. The solvent is then distilled under vacuum and the crude is analyzed by gas chromatography. The molar yield in dodecalactam is 75% with a selectivity of 100%. Table 1 summarizes and compares the results of examples 1, 4 and 5.
Tabla 1.Table 1.
Figure imgf000010_0001
Ej emplo 6
Figure imgf000010_0001
Ex emplo 6
En este ejemplo se describe la obtención de la dodecalactama a partir de la ciclododecanona oxima utilizando un silicato nanolaminar del tipo ITQ-18 (Si/Al =50) en una relación en peso con respecto a la oxima deThis example describes the obtaining of dodecalactam from cyclododecanone oxime using a nanolaminar silicate of the type ITQ-18 (Si / Al = 50) in a weight ratio with respect to the oxime of
2:1.2: 1.
Antes de su uso, el catalizador en una relación en peso con respecto a la oxima de la ciclododecanona de 2:1, se activa por calentamiento a 300 °C bajo una presión de 133,21 Pa (1 Tor) durante 2h. El catalizador se añade a una disolución de oxima (lg) en benzonitrilo (200 mL) . La suspensión resultante se calienta a la temperatura de 130 °C a presión atmosférica durante 5h en un reactor discontinuo bajo agitación. El disolvente se evapora por destilación a vacío y el crudo se analiza por cromatografía de gases. El rendimiento molar en dodecalactama es de 95 % con una selectividad del 100%. Before use, the catalyst in a weight ratio with respect to the cyclododecanone oxime of 2: 1, is activated by heating at 300 ° C under a pressure of 133.21 Pa (1 Tor) for 2h. The catalyst is added to a solution of oxime (lg) in benzonitrile (200 mL). The resulting suspension is heated at a temperature of 130 ° C at atmospheric pressure for 5 hours in a batch reactor under stirring. The solvent is evaporated by vacuum distillation and the crude is analyzed by gas chromatography. The molar yield in dodecalactam is 95% with a selectivity of 100%.

Claims

Reivindicaciones Claims
1. Un procedimiento para la preparación de dodecalactama, caracterizado porque comprende poner en contacto la oxima de la ciclododecanona con un silicato nanolaminar con carácter ácido que posee una relación TIV/Tιπ comprendida entre 15 y 50, en donde TIV representa uno o más cationes tetravalentes distintos de silicio, y T111 representa uno o más cationes trivalentes.1. A process for the preparation of dodecalactam, characterized in that it comprises contacting the oxime of the cyclododecanone with an acidic nanolaminar silicate having a T IV / T ιπ ratio between 15 and 50, where T IV represents one or more tetravalent cations other than silicon, and T 111 represents one or more trivalent cations.
2. Un procedimiento según la reivindicación 1 caracterizado porque TIV representa uno o más cationes tetravalentes seleccionados entre Ge, Ti, Sn y mezclas de ellos .2. A process according to claim 1 characterized in that T IV represents one or more tetravalent cations selected from Ge, Ti, Sn and mixtures thereof.
3. Un procedimiento según la reivindicación 1 caracterizado porque T111 representa uno o más cationes trivalentes seleccionados entre Al, B, Fe, Ga y mezclas de ellos .3. A method according to claim 1 characterized in that T 111 represents one or more trivalent cations selected from Al, B, Fe, Ga and mixtures thereof.
4. Un procedimiento según la reivindicación 1 caracterizado porque el silicato nanolaminar posee un área superficial de 500 m2/g o superior.4. A process according to claim 1 characterized in that the nanolaminar silicate has a surface area of 500 m 2 / g or greater.
5. Un procedimiento según una de las reivindicaciones 1 a 3, caracterizado porque el silicato nanolaminar es del tipo ITQ-2.5. A process according to one of claims 1 to 3, characterized in that the nanolaminar silicate is of the ITQ-2 type.
6. Un procedimiento según una de las reivindicaciones 1 a 3, caracterizado porque el silicato nanolaminar es del tipo ITQ-6. 6. A process according to one of claims 1 to 3, characterized in that the nanolaminar silicate is of the ITQ-6 type.
7. Un procedimiento según una de las reivindicaciones 1 a 3, caracterizado porque el silicato nanolaminar es del tipo ITQ-18.7. A process according to one of claims 1 to 3, characterized in that the nanolaminar silicate is of the ITQ-18 type.
8. Un procedimiento según una de las reivindicaciones 1 a 3, caracterizado porque el silicato nanolaminar es del tipo ITQ-20.A method according to one of claims 1 to 3, characterized in that the nanolaminar silicate is of the ITQ-20 type.
9. Un procedimiento según una de las reivindicaciones anteriores, caracterizado porque se realiza en un reactor seleccionado entre un reactor continuo de tanque agitado, o en un reactor discontinuo de lecho fijo, un reactor discontinuo de lecho móvil fluidizado, y un reactor de tipo riser .A method according to one of the preceding claims, characterized in that it is carried out in a reactor selected from a continuous stirred tank reactor, or in a discontinuous fixed bed reactor, a discontinuous fluidized moving bed reactor, and a riser type reactor .
10. Un procedimiento según una de las reivindicaciones anteriores, caracterizado porque se realiza en presencia de un disolvente, a una presión inferior a 20 xlO5 Pa y a una temperatura entre 40 y 350°C.10. A process according to one of the preceding claims, characterized in that it is carried out in the presence of a solvent, at a pressure of less than 20 x 5 Pa and at a temperature between 40 and 350 ° C.
11. Un procedimiento según la reivindicación 10, caracterizado porque se realiza a una temperatura entre 100 y 300 °C.11. A method according to claim 10, characterized in that it is carried out at a temperature between 100 and 300 ° C.
12. Un procedimiento según una de las reivindicaciones anteriores, caracterizado porque se realiza en fase gas o en fase líquida.12. A method according to one of the preceding claims, characterized in that it is carried out in the gas phase or in the liquid phase.
13. Un procedimiento según la reivindicación 12, caracterizado porque se realiza en fase gas o en fase líquida y porque se realiza en presencia de un nitrilo como disolvente . 13. A process according to claim 12, characterized in that it is carried out in the gas phase or in the liquid phase and in that it is carried out in the presence of a nitrile as solvent.
14. Un procedimiento según la reivindicación 13, caracterizado porque dicho nitrilo es un nitrilo aromático o un nitrilo alifático.14. A process according to claim 13, characterized in that said nitrile is an aromatic nitrile or an aliphatic nitrile.
15. Un procedimiento según la reivindicación 13, caracterizado porque dicho nitrilo está seleccionado entre benzonitrilo, aadiponitrilo y 3-metoxi-propanonitrilo .15. A process according to claim 13, characterized in that said nitrile is selected from benzonitrile, aadiponitrile and 3-methoxy-propanonitrile.
16. Un procedimiento según la reivindicación 12, caracterizado porque se realiza en fase líquida y se utiliza un disolvente seleccionado entre un hidrocarburo aromático, un hidrocarburo aromático halogenado, un dialquilsulfoxido, una N,N-dialquilamida, un alcohol, y un sulfolano.16. A process according to claim 12, characterized in that it is carried out in the liquid phase and a solvent selected from an aromatic hydrocarbon, a halogenated aromatic hydrocarbon, a dialkylsulfoxide, an N, N-dialkylamide, an alcohol, and a sulfolane is used.
17. Un procedimiento según la reivindicación 16, caracterizado porque se realiza en fase líquida en presencia de un disolvente seleccionado entre benceno, tolueno, dimetilsulfóxido, dietilsulfóxido, dimetilformamida, dietilformamida, clorobenceno y diclorobenceno .17. A process according to claim 16, characterized in that it is carried out in the liquid phase in the presence of a solvent selected from benzene, toluene, dimethylsulfoxide, diethylsulfoxide, dimethylformamide, diethylformamide, chlorobenzene and dichlorobenzene.
18. Un procedimiento según la reivindicación 12, caracterizado porque se realiza en fase gaseosa, en presencia de un disolvente seleccionado entre un hidrocarburo aromático y un alcohol.18. A process according to claim 12, characterized in that it is carried out in the gas phase, in the presence of a solvent selected from an aromatic hydrocarbon and an alcohol.
19. Un procedimiento según la reivindicación 18, caracterizado porque el disolvente está seleccionado entre benceno, tolueno, metanol, butanol, pentanol, y hexanol.19. A process according to claim 18, characterized in that the solvent is selected from benzene, toluene, methanol, butanol, pentanol, and hexanol.
20. Un procedimiento según la reivindicación 1, caracterizado porque el catalizador se utiliza en una proporción en peso con respecto a la oxima entre 0.1:1 y 6:1.20. A process according to claim 1, characterized in that the catalyst is used in a weight ratio with respect to the oxime between 0.1: 1 and 6: 1.
21. Un método según una de las reivindicaciones anteriores, en el que el catalizador se regenera tras su uso mediante una operación seleccionada entre lavado con un disolvente, calcinación a temperaturas entre 450 y 500 °C, y ambas . 21. A method according to one of the preceding claims, wherein the catalyst is regenerated after use by an operation selected from washing with a solvent, calcination at temperatures between 450 and 500 ° C, and both.
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Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2887250A1 (en) * 2005-06-21 2006-12-22 Arkema Sa Preparation of lauryl lactam by a Beckmann rearrangement of cyclododecanone oxime in gaseous phase at a specific temperature in the presence of a zeolite catalyst
AP3776A (en) * 2009-04-24 2016-08-31 Iceutica Pty Ltd Production of encapsulated nanoparticles at commercial scale

Families Citing this family (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
ES2257202B1 (en) * 2004-11-18 2007-07-16 Ube Corporation Europe, S.A. PROCEDURE FOR OBTAINING DODECALACTAMA IN THE PRESENCE OF IONIC LIQUIDS.
ES2257950B1 (en) * 2004-12-01 2007-07-16 Ube Corporation Europe, S.A. PROCEDURE FOR THE PREPARATION OF OXYMES CATALYZED BY A LAMINAR LAMINATED MATERIAL.

Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3418314A (en) * 1964-02-26 1968-12-24 Bayer Ag Process for the production of lactams
US3503958A (en) * 1964-10-29 1970-03-31 Mobil Oil Corp Molecular rearrangement of oximes
US5227028A (en) * 1990-07-06 1993-07-13 Dsm N.V. Process for treating amides
WO2001021305A1 (en) * 1999-09-21 2001-03-29 Korea Institute Of Science And Technology Layered silicate catalysts pillared with metal oxide

Patent Citations (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3418314A (en) * 1964-02-26 1968-12-24 Bayer Ag Process for the production of lactams
US3503958A (en) * 1964-10-29 1970-03-31 Mobil Oil Corp Molecular rearrangement of oximes
US5227028A (en) * 1990-07-06 1993-07-13 Dsm N.V. Process for treating amides
WO2001021305A1 (en) * 1999-09-21 2001-03-29 Korea Institute Of Science And Technology Layered silicate catalysts pillared with metal oxide

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
CORMA A. ET AL: "Active sites for the liquid-phase Beckmann rearrangement of Cyclohexanone, Acetophenone and Cyclododecanone Oximes, catalyzed by Beta Zeolites", JOURNAL OF CATALYSIS, vol. 177, 1998, pages 267 - 272, XP005291917, DOI: doi:10.1006/jcat.1998.2110 *
CORMA A. ET AL: "Novel delaminated zeolites are more active acid catalysts than conventional zeolites and mesoporous AL/MCM-41 for the synthesis of fine chemicals", STUDIES IN SURFACE SCIENCE AND CATALYSIS, vol. 135, 2001, pages 3719 - 3726 *

Cited By (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
FR2887250A1 (en) * 2005-06-21 2006-12-22 Arkema Sa Preparation of lauryl lactam by a Beckmann rearrangement of cyclododecanone oxime in gaseous phase at a specific temperature in the presence of a zeolite catalyst
WO2006136699A3 (en) * 2005-06-21 2007-04-12 Arkema France Method for synthesising lauryl lactam (l12) by catalytically rearranging cyclododecanone oxime in a gaseous phase
JP2008546743A (en) * 2005-06-21 2008-12-25 アルケマ フランス Method for synthesizing lauryl lactam (L12) by gas phase catalytic rearrangement of cyclododecanone oxime
KR101011962B1 (en) 2005-06-21 2011-01-31 아르끄마 프랑스 Method for synthesising lauryl lactam l12 by catalytically rearranging cyclododecanone oxime in a gaseous phase
US7893255B2 (en) 2005-06-21 2011-02-22 Arkema France Process for the synthesis of lauryllactam (L12) by gas phase catalytic rearrangement of cyclododecanone oxime
AP3776A (en) * 2009-04-24 2016-08-31 Iceutica Pty Ltd Production of encapsulated nanoparticles at commercial scale

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