Classifications

• • 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 process for the cyclizing hydrolysis of an aminonitrile compound into lactam in the presence of a catalyst.
• It relates more particularly to a process for the cyclizing hydrolysis of an aminonitrile compound into lactam in the presence of a solid catalyst of the clay type.
• Lactams such as epsilon-caprolactam
• one of the processes is the cyclizing hydrolysis of the corresponding aminonitrile , and more particularly of a corresponding aliphatic aminonitrile, in the presence of water and a catalyst.
• US Pat. No. 2,357,484 describes a process for the preparation in the vapor phase of lactam, with activated alumina, silica in the form of gel or borophosphoric acid as catalyst.
• US Patent 4,628,085 also describes a process for preparing lactams by cyclizing hydrolysis in the vapor phase in the presence of a silica-based catalyst, with a specific surface area greater than 250 m 2 / g. This reaction is carried out in the presence of hydrogen and ammonia.
• Application WO 98/0669 proposes catalysts based on metal oxides, hydrated or not, the metals being selected from the group comprising tin, zirconium, hafnium, bismuth, vanadium, niobium, tantalum or their mixtures.
• the cycle time of these catalysts is very short and incompatible with industrial exploitation of the lactam manufacturing process.
• Application WO96 / 22974 proposes a process for the cyclizing hydrolysis of aminonitrile in the vapor phase using as an catalyst an alumina having specific surface areas and determined pore volume.
• Metallic phosphates and zeolites are also known catalysts for the reaction for preparing lactams by cyclizing hydrolysis.
• the catalysts used in the processes of the prior art exhibit good initial activity and make it possible to obtain good selectivity for the reaction for converting aminonitrile into lactam.
• the subject of the invention is a process for the cyclizing hydrolysis of an aminonitrile compound into lactam by reaction of an aminonitrile of general formula (I) below: N ⁇ C - R - NH 2 (I) in which :
• R represents an aliphatic, cycloaliphatic, arylaliphatic, saturated or unsaturated, linear or branched, substituted or unsubstituted radical comprising from 1 to 12 carbon atoms, with water, in the presence of a solid catalyst, characterized in that the catalyst is a clay.
• Clays are phyllosilicates which are classified by groups according to their nature and their physicochemical properties, groups among which we can cite kaolins, serpentines, smectites or montmorillonites, illites or micas, glauconites, chlorites or vermiculites, attapulgites or sepiolite, mixed-layer clays, allophanes or imogolites and clays with a high alumina content.
• Certain clays have a lamellar structure with an expandable network. They have the particularity of adsorbing various solvents, in particular water, between the sheets which compose them, which causes swelling of the solid as a result of the weakening of the electrostatic connections between the sheets. These clays essentially belong to the group of smectites (or group of montmorillonite) and for some of them to the group of vermiculites.
• Their structure is composed of “elementary” sheets with three layers: two simple layers of SiO 4 tetrahedra in which part of the silicon can be replaced by other cations in tetrahedral position such as Al 3+ or possibly Fe 3+ , and between these two layers of tetrahedra, a layer of oxygen octahedra at the center of which are metal cations such as Al 3+ , Fe 3+ , Mg 2+ .
• This octahedral layer consists of a compact stack of oxygen either from the vertices of the preceding tetrahedra or from OH hydroxyl groups.
• the compact hexagonal network of these oxygen contains 6 octahedral cavities.
• the layer When the metal cations occupy 4 of these cavities (2 cavities out of 3 as in the case of aluminum for example), the layer is said to be dioctahedral; when they occupy all the cavities (3 cavities out of 3 as in the case of magnesium for example), the layer is said to be trioctahedral.
• the elementary sheets of these clays carry negative charges which are compensated for by the presence of exchangeable, alkaline cations such as Li + , Na + , K + , alkaline earths such as Mg 2+ , Ca 2+ , and possibly the hydronium ion H 3 O + .
• the smectites have charge densities on the sheets lower than those of clays of the vermiculite type: approximately 0.66 charge per elementary mesh against 1 to 1.4 charge per elementary mesh for the vermiculites.
• the compensating cations are essentially sodium and calcium in smectites, magnesium and calcium in vermiculites. From the point of view of charge densities, smectites and vermiculites are intermediate between talc and pyrophyllite on the one hand, whose sheets are neutral and micas on the other hand, characterized by a high charge density on the sheets (approximately 2 per elementary mesh) generally compensated by K + ions.
• interfoliar cations of smectites and vermiculites can be fairly easily replaced by ion exchange by other cations such as, for example, ammonium ions or ions of alkaline earth metals or rare earth metals.
• the swelling properties of clays depend on various factors including the charge density and the nature of the compensating cation.
• smectites whose charge density is lower than that of vermiculites have swelling properties clearly superior to those of the latter, and therefore constitute a very interesting class of solids.
• the repetitive distance or basal spacing represents the shortest distance separating two crystallographically identical patterns located in two adjacent sheets.
• the basic spacing of the smectites can thus reach, by swelling, values ranging from about 1 nm to more than 2 nm.
• the interfoliar spacing (between two sheets) is maximum. It can reach a value close to 1 nm.
• the clay which constitutes the catalyst for cyclizing hydrolysis of aminonitrile into lactam is a smectite. More preferably, the clay is montmorillonite. Some clays unfortunately have the drawback of losing their expanded character by heating to 100 ° C. and therefore of not preserving the increase in specific surface resulting from their expansion. This is particularly the case for smectites.
• a method consisting in introducing bridges constituted by oligomers of a hydroxide of a metal, in particular aluminum hydroxide, has been described by LAHAV, SHAMI and SHABTAI in Clays and Clays Ore, vol. 26 (n ° 2 ), p. 107-115 (1978) and in French patent 2,394,324.
• the formation of bridges consisting of oligomers of mixed hydroxides of silicon and boron is described in US Pat. No. 4,248,739.
• a technique for bridging smectites, by dialysis, using aluminum hydroxides, chromium, zirconium and titanium, etc. is claimed in patent EP 0.073.718.
• These methods consist in principle of bringing the clay into contact with a solution containing more or less oligomerized ionic species of the hydroxyaluminic type (in the case of aluminum). This operation is generally carried out in a slightly concentrated solution, at a temperature below 80 ° C. and if possible in the absence of cloudiness consisting of the start of precipitation of the metal hydroxide.
• concentrations of metal ion and clay must be optimized so that sufficient solid pillars are formed and the porosity of the clay is not greatly reduced by the insertion of too much metal oxide.
• the bridged smectites acquire a strong acidity although globally lower than those of conventional zeolites of type Y or mordenite for example.
• the clay used as catalyst for the cyclizing hydrolysis of aminonitrile into lactam is bridged.
• the catalyst can comprise, in addition to a clay, one or more other metallic compounds, often called dopants, such as for example chromium, titanium, molybdenum, tungsten, iron, zinc.
• dopants such as for example chromium, titanium, molybdenum, tungsten, iron, zinc.
• the chromium and / or iron and / or titanium compounds are considered to be the most advantageous.
• These dopants usually represent, by weight per weight of clay, from 0% to 10% and preferably from 0% to 5%.
• metal compound means both the metal element and the metal ion or any combination comprising the metal element.
• the clay according to the invention can be calcined, according to a technique known to those skilled in the art.
• the catalyst is used in the form of balls, crushed, extruded in the form of cylindrical granules or of hollow or full multilobed form or of honeycombs, pellets.
• the shaping can optionally be carried out using a binder. It can first of all be clay beads obtained from oil-drop shaping
• This type of beads can for example be prepared by a process similar to that described for the formation of alumina beads in patents EP-A-0 015 801 or EP-A-0 097 539.
• the control of the porosity can be produced in particular, according to the method described in patent EP-A-0 097 539, by coagulation in drops of a suspension, of an aqueous dispersion of clay.
• the balls can also be obtained by the agglomeration process in a bezel or rotating drum.
• extruded clay can also be extruded clay. These can be obtained by mixing, then extruding a clay-based material.
• the porosity of these extrusions can be controlled by the choice of clay used and by the conditions of preparation of this clay or by the conditions of kneading of this clay before extrusion.
• the clay can thus be mixed during mixing with porogens.
• the extrusions can be prepared by the process described in US Pat. No. 3,856,708.
• beads with controlled porosity can be obtained by addition of porogen and agglomeration in a rotating bowl or a beverage pan or by 'Oil-drop' process.
• the cyclizing hydrolysis reaction can be carried out with a minimum of side reactions, with good selectivity of the lactam process and therefore the purity of the crude product obtained.
• the aminonitriles which can be cyclized by the process of the invention are advantageously aliphatic ⁇ -aminonitriles such as ⁇ -aminovaleronitrile, ⁇ -aminocapronitrile, ⁇ -aminooctanitrile, ⁇ -aminononanitrile, ⁇ -aminodecanitrile, ⁇ -aminodecanonitrile, ⁇ -aminododecanonitrile, methyl-aminovaleronitrile.
• the preferred and most important compound is amino-6 capronitrile which leads to ⁇ -caprolactam.
• the latter compound is the polyamide 6 monomer used for the manufacture of various articles such as moldings, threads, fibers, filaments, cables or films.
• the ⁇ -caprolactam produced by the cyclizing hydrolysis reaction is advantageously purified by the various known purification methods, such as distillation, crystallization in a solvent medium or in the molten phase, treatment on resin, treatment with an oxidant and / or hydrogenation. These different stages can be partially or totally combined in different orders and according to the degree of purity of the ⁇ -caprolactam produced.
• the cyclizing hydrolysis reaction requires the presence of water.
• the molar ratio between the water and the aminonitrile used is usually between 0.5 and 50 and preferably between 1 and 20. The higher value of this ratio is not critical for the invention, but higher ratios have little interest in economic matters.
• the cyclizing hydrolysis reaction is carried out in the vapor phase.
• the reactants are maintained in the vapor state in the reactor loaded with a determined quantity of catalyst.
• the aminonitrile and the water can be used in the form of their mixtures in the vapor state or can be introduced separately into the reactor.
• the reagents can be pre-evaporated, which then circulate in a mixing chamber.
• the cyclizing hydrolysis reaction is carried out in the liquid phase.
• the aminonitrile and water reagents are used in the liquid state under pressure, optionally in the presence of a solvent.
• the free volume of the reactor can be occupied by an inert solid such as, for example, quartz, in order to promote the vaporization and the dispersion of the reactants.
• an inert solid such as, for example, quartz
• any inert gas can be used without disadvantage as a carrier, such as nitrogen, helium or argon.
• the temperature at which the vapor phase process is carried out is advantageously sufficient for the reactants to be in the vapor state. It is generally between 200 ° C and 450 ° C and preferably between 250 ° C and 400 ° C.
• reaction is carried out under pressure.
• the contact time between the aminonitrile and the catalyst is not critical. It can vary depending on the equipment used in particular. This contact time is preferably between 0.5 and 200 seconds and even more preferably between 1 and 100 seconds.
• Pressure is not a critical process parameter.
• the method will be implemented under a pressure of 0.1 to 20 bar.
• this pressure is advantageously between 10 " 3 bar and 3 bar.
• an inert solvent under the reaction conditions such as for example an alkane, a cycloalkane, an aromatic hydrocarbon or one of these preceding halogenated hydrocarbons, and thus to have a liquid phase in the reaction flow.
• the reactor thus charged is heated to 300 ° C. under a stream of nitrogen (with a flow rate of 5.2 liters / hour) for 2 hours.
• a mixture of 6-amino-capronitrile (ACN) and water (water / ACN molar ratio of 4.1) is then injected using a pump.
• the speed of injection of the mixture is 4.34 ml / h.
• the vapors are condensed in a glass trap at room temperature over a period of 2 hours: the reaction product is thus recovered in two successive sections of 1 hour.
• the final reaction mixture (the second fraction taken) is assayed by vapor phase chromatography in particular to determine the concentration of caprolactam.
• the transformation rate (TT) of aminocapronitrile, the selectivity is determined
• RT in caprolactam (CPL) relative to the transformed aminocapronitrile

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• Chemical & Material Sciences (AREA)
• Organic Chemistry (AREA)
• Catalysts (AREA)
• Low-Molecular Organic Synthesis Reactions Using Catalysts (AREA)
• Other In-Based Heterocyclic Compounds (AREA)
• Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)

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• 2001
  • 2001-03-21 FR FR0103826A patent/FR2822465A1/fr active Pending
• 2002
  • 2002-03-19 RU RU2003130972/04A patent/RU2003130972A/ru unknown
  • 2002-03-19 BR BR0208606-9A patent/BR0208606A/pt not_active IP Right Cessation
  • 2002-03-19 EP EP02753580A patent/EP1370524A1/fr not_active Withdrawn
  • 2002-03-19 PL PL02365252A patent/PL365252A1/xx unknown
  • 2002-03-19 HU HU0303591A patent/HUP0303591A3/hu unknown
  • 2002-03-19 MX MXPA03008451A patent/MXPA03008451A/es not_active Application Discontinuation
  • 2002-03-19 KR KR10-2003-7012286A patent/KR20030093264A/ko not_active Application Discontinuation
  • 2002-03-19 WO PCT/FR2002/000957 patent/WO2002074739A1/fr not_active Application Discontinuation
  • 2002-03-19 US US10/472,473 patent/US20040116691A1/en not_active Abandoned
  • 2002-03-19 CA CA002441812A patent/CA2441812A1/fr not_active Abandoned
  • 2002-03-19 IL IL15801802A patent/IL158018A0/xx unknown
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