EP2958673A1 - Gas-phase and liquid-gas-phase nitrilation process - Google Patents

Gas-phase and liquid-gas-phase nitrilation process

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Publication number
EP2958673A1
EP2958673A1 EP14705194.0A EP14705194A EP2958673A1 EP 2958673 A1 EP2958673 A1 EP 2958673A1 EP 14705194 A EP14705194 A EP 14705194A EP 2958673 A1 EP2958673 A1 EP 2958673A1
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EP
European Patent Office
Prior art keywords
oxides
catalyst
metal
oxide
nitrilation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
Application number
EP14705194.0A
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German (de)
French (fr)
Inventor
Jean-Luc Dubois
Adrien MEKKI-BERRADA
Aline AUROUX
Simona BENNICI
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Arkema France SA
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Arkema France SA
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Publication date
Application filed by Arkema France SA filed Critical Arkema France SA
Publication of EP2958673A1 publication Critical patent/EP2958673A1/en
Ceased legal-status Critical Current

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    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C253/00—Preparation of carboxylic acid nitriles
    • C07C253/22—Preparation of carboxylic acid nitriles by reaction of ammonia with carboxylic acids with replacement of carboxyl groups by cyano groups
    • 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
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/066—Zirconium or hafnium; Oxides or hydroxides thereof
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/835—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with germanium, tin or lead
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/847—Vanadium, niobium or tantalum or polonium
    • B01J23/8474—Niobium
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/847—Vanadium, niobium or tantalum or polonium
    • B01J23/8476—Tantalum
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/643—Pore diameter less than 2 nm
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/66—Pore distribution
    • 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
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/04—Mixing
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/19—Catalysts containing parts with different compositions

Definitions

  • the invention relates to a method of nitrilation in the gas phase and mixed liquid-gas phase from fatty acid esters or fatty acids implementing a specific solid catalyst based on a mixture of metal oxides.
  • the invention also relates to a specific catalyst, its method of preparation and its use.
  • nitriles and / or fatty amines from fatty acids extracted from vegetable or animal oils are known. This process is described in the Kirk-Othmer Encyclopedia Vol 2, 4 ° Edition, page 411.
  • the fatty amine is obtained in several stages.
  • the first step consists of methanolysis or hydrolysis of a vegetable oil or an animal fat respectively producing the methyl ester of a fatty acid or a fatty acid.
  • the methyl ester of the fatty acid can then be hydrolysed to form the fatty acid.
  • the fatty acid is converted to nitrile by reaction with ammonia, and finally to amine by hydrogenation of the nitrile thus obtained.
  • the invention relates to a method for the nitrilation of the acid function or the ester function, depending on the reagent used, optionally unsaturated.
  • the reaction scheme for the synthesis of nitriles from a fatty acid can be summarized as follows:
  • nitrilation means a reaction between a fatty acid or a fatty acid ester and ammonia leading to the conversion of the function C0 2 H or C0 2 R, respectively, in CN function. This nitrilation reaction is also called ammoniation because this reaction involves ammonia.
  • the fatty acid or a mixture of fatty acids is charged with a catalyst, which is generally a metal oxide, and most frequently zinc oxide.
  • the reaction medium is brought to about 150 ° C. with stirring, and ammonia gas is then introduced.
  • an ammonium salt or ammonium soap is formed.
  • the temperature of the reaction medium is then raised to around 250 ° C.-300 ° C., still under the introduction of ammonia.
  • the ammonium salt is converted to amide with release of a first molecule of water.
  • the amide is transformed into nitrile with formation of a second molecule of water.
  • This formed water is continuously removed from the reactor by driving unreacted ammonia and some of the lighter fatty chains.
  • Liquid phase processes using batch reactors, require very long reaction times, especially several hours.
  • the feed is vaporized and brought into contact with ammonia, the temperature of which is between 250 ° C and 600 ° C, in the presence of a catalyst.
  • This catalyst is generally chosen from the family of metal oxides consisting of metal oxides, taken alone or as a mixture, such as Zr, Ta, Ga In, Se, Nb, Hf, Fe, Zn, Sn or alumina. , an oxide of thorium, and in particular doped alumina.
  • the gas phase processes are carried out continuously at a temperature of the order of 300 ° C., and under these conditions the contact times are of the order of a few seconds on the catalyst. However, as soon as the temperature decreases, with the known catalysts, the conversions fall, and it is then necessary to increase the average contact time to find high conversions.
  • the Applicant observed that the nitrilation stage played an important role, especially when it was carried out on a ⁇ -unsaturated acid. Indeed, the lo calization of the double bond at the end of the chain and therefore poorly protected, leads to the formation of isomers as a result of displacement of the double bond. Having observed these phenomena, she found that this disadvantage could be largely limited by working with the ester rather than the corresponding acid which made it possible to operate in "softer" conditions. Since the boiling point of the ester is lower than that of the corresponding acid, it is possible to reach higher vapor pressures with the ester. In addition, by operating in a reactor operating continuously, either in the gas phase or in the mixed liquid-gas phase, the residence time of the reactants in contact with the catalysts being much smaller than in the conventional liquid phase (batch) allows limit isomerization during the process.
  • the aim is to obtain a process leading to an excellent conversion rate, with an excellent yield, by reducing the content of by-products resulting from the migration of the double bond, when the reagent used is unsaturated, decreasing the by-product content resulting from the methylation of the intermediate amide, when the reagent used is a methyl ester, and to reduce the content of intermediate amide.
  • the object of the invention is a process for the nitrilation of fatty acid or fatty acid ester, which may be unsaturated, by the action of ammonia in a reactor operating continuously in the gas phase or in the mixed gas - liquid phase in a reactor a temperature range of 1 80 to 400 ° C, in the presence of a solid catalyst comprising:
  • At least one metal oxide chosen from aluminum oxides, zirconium oxides, niobium oxides, tantalum oxides and tin oxides,
  • the metal oxide or oxides, the metal of which belongs to column 8 being present in a volume ratio of 0.1 to 0.6 relative to the volume of the mixture of all the metal oxides.
  • the invention also relates to a solid catalyst comprising at least one metal oxide, the metal of which belongs to column 8 of the periodic table in admixture with at least one metal oxide chosen from aluminum oxides, oxides and of zirconium, niobium oxides, tantalum oxides and tin oxides, the metal oxide or oxides, the metal of which belongs to column 8 being present in a volume ratio of 0.1 to 0.6 relative to to the volume of the mixture of all the metal oxides.
  • the invention relates to the process for the preparation of this catalyst as well as the use of this catalyst in nitrilation processes.
  • any range of values designated by the expression "between a and b" represents the range of values from more than a to less than b (i.e., excluding terminals a and b), while that any range of values designated by the expression “from a to b” means the range of values from a to b (that is, including the strict limits a and b).
  • the term "gas-liquid mixed phase” is intended to mean a process employing a mixed gas-liquid fluid including a liquid as a continuous phase and a gas as a dispersed phase or a liquid as a dispersed phase and a gas as a continuous phase.
  • a trickle bed configuration in a rising bed of liquid and fixed bed catalyst, it has a submerged bed configuration.
  • the reactor can also operate in fluidized bed mode. In this configuration, the catalyst is maintained fluidized not only by the gas flow, but also by the vaporization of the liquid charge which thus generates a large volume of gas.
  • the invention relates to a method for the nitrilation of fatty acid or fatty acid ester, optionally unsaturated, by the action of ammonia in a reactor operating continuously in the gas phase or in the mixed gas - liquid phase in a range.
  • temperature ranging from 1 80 to 400 ° C in the presence of a solid catalyst comprising at least one metal oxide, the metal of which belongs to column 8 of the periodic table in admixture with at least one metal oxide chosen from oxides of aluminum, zirconium oxides, niobium oxides, tantalum oxides and tin oxides, the metal oxide or oxides, the metal of which belongs to column 8 being present in a volume ratio of 0.1 at 0.6 relative to the volume of the mixture of all the oxides.
  • the reagents of the nitrilation process according to the invention may be fatty acids or esters, optionally unsaturated, preferably ⁇ -unsaturated.
  • fatty is understood to mean an acid or an ester comprising a carbon chain, saturated or unsaturated, linear having from 8 to 36 carbon atoms.
  • acids and esters which are useful for the process of the invention are of the following formula:
  • n the integer 7 or 8
  • R represents either a hydrogen atom or an alkyl radical having 1 to 4 carbon atoms.
  • the process of the invention uses as acids ou-unsaturated acids or esters having either 10 atoms or 1 carbon atoms per molecule.
  • the former in particular methyl 9-decenoate, are marketed in the form of esters by ELEVANCE Renewable Sciences.
  • the latter in particular methyl 10-undecenoate, are manufactured by the company Arkema as part of its castor oil-based process, the methyl undecylenate being obtained after pyrolysis.
  • the nitrilation step is carried out in a reactor operating continuously, that is to say in which the reactants that are initially gaseous, solid or liquid are introduced (and the extracted products) into the reactor. continuous according to predetermined rates.
  • the method of nitrilating fatty acids and esters is conducted at a reaction temperature of from 180 to 400 ° C, and preferably from 200 to 300 ° C and more preferably from 200 to 250 ° C.
  • the charge of fatty acids or fatty esters, optionally unsaturated, is vaporized and brought to a temperature ranging from 180 ° to 350 ° C. in contact with ammonia, the introduction temperature of which is 150 ° to 600 ° C.
  • the pressure exerted in the reactor can range from 0.1 to 10 atmospheres (absolute), and preferably from 0.5 to 5 atm, and even more preferably from 1 to 3 atm.
  • the molar ratio NH 3 / fatty ester or NH 3 / fatty acid of the reactants may range from 1 to 50, preferably from 3 to 30, and even more preferably from 5 to 20.
  • the two reagents can be introduced into the reactor in the gaseous state (pure gaseous phase).
  • the fatty acid or ester, optionally unsaturated is vaporized and brought to a temperature ranging from 1 80 to 350 ° C in contact with with ammonia, whose introduction temperature is from 150 to 600 ° C. and at a pressure ranging from 0.1 to 10 atmospheres (absolute), preferably from 0.5 to 5 atmospheres and even more preferably from 1 to 3 atmospheres.
  • the rates of introduction of the reagents are such that the contact time with the solid catalyst ranges from 1 second to 300 seconds.
  • the mixed phase nitrilation process is carried out with the fatty acids.
  • the ammonia is introduced in the form of a gas
  • the acid is introduced, after possible preheating, into the reactor near the catalytic bed, at least partly in the form of a gas.
  • liquid at a rate determined to flow in the form of a film (dripping bed) on the heated catalyst bed in contact with which a fraction of the liquid is vaporized.
  • the reaction or series of reactions is carried out in contact with the catalyst surface or in its immediate vicinity. This so - called "trickling bed” technique is well known and widely used in the oil industry.
  • the ammonia stream can be co-current or countercurrent to the flow of the acid.
  • the rate of introduction of the acid is such that the average contact time of the liquid phase in the reactor is less than 1 hour, and preferably less than 30 minutes.
  • This contact time is determined by the following calculation: volume of catalyst (in liters) / flow rate of the acid (in liquid liters at 25 ° C. per hour), ie the inverse of the hourly liquid liquid hourly velocity.
  • the gaseous stream and the liquid flow are descending, or in countercurrent, the gaseous flow being ascending and the liquid flow descending.
  • the countercurrent version, rising gas and descending acid may be particularly advantageous for limiting the hydrolysis of the formed nitrile.
  • the ammonia is injected in the foot, the water and the alcohol come out at the head, the acid enters the head and the nitrile comes out in the foot. So in the foot, it has a high concentration of nitrile and ammonia and at the head a high concentration of water and alcohol, and less ammonia. The equilibrium can thus be displaced, in particular that of the hydrolysis of the nitrile which gives back acid.
  • the present invention also relates to a solid catalyst.
  • the solid catalyst according to the present invention comprises
  • At least one metal oxide chosen from aluminum oxides, zirconium oxides, niobium oxides, tantalum oxides and tin oxides,
  • the metal oxide or oxides, the metal of which belongs to column 8 being present in a volume ratio of 0.1 to 0.6 relative to the volume of the mixture of all the metal oxides.
  • the metal oxide is an iron oxide. It is especially chosen from FeO, Fe 3 C 4 and Fe 2 O 3.
  • the metal oxide whose metal belongs to column 8 of the table of the preferred periodic table is ferric oxide: Fe 2 O 3 .
  • the metal oxides chosen from aluminum oxides, zirconium oxides, niobium oxides, tantalum oxides and tin oxides are chosen from aluminum oxides, zirconium oxides and oxides. of niobium. More particularly, they are chosen from aluminum oxide: Al 2 O 3 , zirconium oxide ZrO 2 , and niobium pentoxide: Nb 2 O 5 .
  • the alumina used is alumina gamma marketed by the company BASF under the commercial reference AL-3996, or by the companies Axens and Saso l.
  • the zirconia (ZrO 2 ) used is sold by the companies Norpro-StGobain, Daiichi Kigenso KK, and MEL, Niobium oxide (Nb 2 0 5 ) is marketed by the companies STARCK and CBMM, and iron oxide III hydrated is marketed among others by Sigma-Aldrich (FeO (OH)) (catalyst grade, 30-50 mesh broken and sieved).
  • the solid catalyst according to the invention comprises the following combinations: ferric oxide: Fe 2 O 3 on a niobium pentoxide support: Nb 2 0 5 ; ferric oxide: Fe 2 O 3 on an aluminum oxide support: Al 2 O 3 and ferric oxide: Fe 2 O 3 on a zirconium oxide support: Zr0 2 .
  • the volume ratio of the metal oxide, the metal of which belongs to column 8 of the table of the periodic table on the volume of the mixture of all the oxides ranges from 0.1 to 0.6.
  • the volumetric ratio of the iron oxide / alumina oxide pair is from 0.2 to 0.5.
  • the volumetric ratio of the iron oxide / zirconium oxide pair ranges from 0.2 to 0.5.
  • the volumetric ratio of the iron oxide / niobium oxide pair ranges from 0.2 to 0.5, especially from 0.25 to 0.4.
  • the catalyst according to the present invention is characterized by a specific surface area ranging from 10 to 500 m 2 / g, and preferably from 40 to 300 m 2 / g, more preferably from 40 to 250 m 2 / g, and in particular from 40 to 250 m 2 / g. 200 m 2 / g.
  • BET specific surface area (Brunauer, Emmett and Teller) means the available surface area per gram of material. This measurement is based on a gas adsorption on the surface of the solids studied. The measurement of the specific surface area is carried out according to ASTM D 3663-84.
  • the catalyst is characterized by a pore size distribution, such that less than 20% of the porous volume is in pores with a diameter of less than 2 nm, and preferably less than 3.5 nm, and even more preferably less than 7 nm.
  • the pore sizes being calculated according to ASTM D4222-83 (Nitrogen adsorption) for porous void distribution measurement and ASTM D4641 -87 for calculating pore size distributions.
  • the catalyst may be in the form of beads, extrudates, pellets, cylindrical, or polylobic, or in the form of a hollow cylinder with one or more holes, or in the form of a cylinder having notches along them. edges, so as to increase the outer surface ratio of the grain relative to the volume of the grain. This criterion is important to reduce diffusional limitations.
  • the grains Preferably, for catalysis on a fixed bed, the grains have a size of 1 to 8 mm, and preferably 3 to 5 mm in their industrial use, dimension along their greatest length.
  • the grains have an average size of 40 to 300 ⁇ , and preferably 80 to 150 ⁇ in their industrial use, the catalysts are preferably in the form of microbeads.
  • a method of preparing the catalysts several methods may be suitable: the coprecipitation of a salt or a mixture of salt; kneading precursors in general in the form of salts, oxides or hydroxides; impregnating a compound with another, for example impregnating aluminum, zirconium or niobium oxides with a solution containing an iron oxide precursor; reactive grinding, in which the two oxides are intimately mixed by vigorous grinding, which leads to the formation of a new compound; or atomization.
  • the precursors of the oxides in different forms can be used in particular in oxide, nitrate, carbonate, chloride, sulfate (including oxysulfate), phosphate, organometallic compound, acetate, acetylacetonate.
  • the preparation of a catalyst from zirconium oxysulphate results in a suitable catalyst for the process of the invention.
  • the mixture of metal oxides according to the present invention is preferably a mechanical mixture.
  • the oxides can be separately ground finely, preferably so as to reach particle sizes ranging from 1 to 8 mm along their greatest length, then measured volumes are mixed and homogenized .
  • the invention finally relates to the use of the catalyst as defined above in a process for the nitrilation of fatty acids or of fatty acid esters.
  • the catalysts used in the examples have the following characteristics, shown in Table 1 below:
  • EXAMPLE 1 Test on the methyl ester of lauric acid.
  • the assembly consists of an evaporation chamber, where the ester is fed continuously in its liquid state via a peristaltic pump.
  • a controlled flow of dry nitrogen leads to the ester and the transports to the catalytic bed below.
  • the controlled flow of ammonia comes to meet the flow of ester + nitrogen at the outcropping of the catalytic bed which is a cylinder of 8 mm diameter by 30 mm retained on a stainless steel frit.
  • the outflow is condensed a first time at 150-170 ° C to recover the lauric (nitriles, amide, acid, methylamide ..), and a second time at 12 ° C and then -77 ° C (via a dry ice trap) ) to condense the light ones.
  • the condensate is removed and analyzed by GC-FID and GC-MS, from which the ester, nitrile and optionally amide and N-methyl amide concentrations are calculated.
  • the metal oxides were separately finely ground and measured volumes were pooled and homogenized.
  • the average residence time is 4.5 seconds.
  • the results in terms of conversion, nitrilation and relative to the formation of the N-methylated by-product, each expressed in molar percentage are shown in the tables below.
  • the catalyst mixture according to the invention leads to an increase for the nitrilation of 71% calculated with respect to the value obtained for the alumina alone and 211%> calculated with respect to the value obtained for iron oxide alone.
  • FIG. 1 provides the proof of the expected effect related to the values of the volume ratio according to the invention.
  • the average residence time is 4.5 seconds.
  • the results in terms of conversion, of nitrilation, each expressed as a percentage of metals are shown in the tables below. 2. At 200 ° C.
  • the catalyst mixture according to the invention leads to an increase for the nitrilation compared to the metal oxides used alone.
  • FIG. 2 provides the proof of the expected effect related to the values of the volume ratio according to the invention.
  • Tests were carried out on the methyl ester of undecenoic acid and with the Fe 2 O 3 catalyst on an Al 2 O 3 support .
  • the procedure is the same as that set forth in Example 1 above.
  • the average residence time is 4.5 seconds.
  • the results in terms of conversion, of nitrilation, each expressed in molar percentage are shown in the tables below.
  • the catalyst mixture according to the invention leads to a surprising and unexpected increase in nitrilation.

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Abstract

The invention relates to a process for nitrilation of a fatty acid or of a fatty acid ester, which is optionally unsaturated, by reacting ammonia in a reactor operating continuously in the gas phase or in the mixed gas-liquid phase in a temperature range of from 180 to 400°C, in the presence of a solid catalyst comprising - at least one metal oxide, the metal of which belongs to column 8 of the Periodic Table, as a mixture with - at least one metal oxide chosen from aluminium oxides, zirconium oxides, niobium oxide, tantalum oxides and tin oxides, wherein the metal oxide(s), the metal of which belongs to column 8, are present in a volume ratio of 0.1 to 0.6 relative to the volume of the mixture of all the oxides.

Description

Procédé de nitrilation en phase gaz et liquide-gaz  Process of nitrilation in gas phase and liquid-gas
Le travail, qui a conduit à cette invention a reçu un financement de la part de l'Union Européenne dans le cadre du 7ième Programme Cadre (FP7/2007-2013) sous le numéro de projet N°241718 EUROBIOREF. The work that led to this invention received funding from the European Union under the 7th Framework Program (FP7 / 2007-2013) under the project number N ° 241718 EUROBIOREF.
L'invention vise un procédé de nitrilation en phase gaz et en phase mixte liquide-gaz à partir d'esters d'acides gras ou d'acides gras mettant en œuvre un catalyseur solide spécifique à base d'un mélange d'oxydes métalliques. L'invention porte également sur un catalyseur spécifique, son procédé de préparation, ainsi que son utilisation.  The invention relates to a method of nitrilation in the gas phase and mixed liquid-gas phase from fatty acid esters or fatty acids implementing a specific solid catalyst based on a mixture of metal oxides. The invention also relates to a specific catalyst, its method of preparation and its use.
Il est connu des procédés de fabrication de nitriles et/ou d'amines gras à partir d'acides gras extraits d'huiles végétales ou animales. Ce procédé est décrit dans l'encyclopédie Kirk-Othmer Vol 2, 4° Edition, page 411. L'amine grasse est obtenue en plusieurs étapes. La première étape consiste en une méthanolyse ou une hydrolyse d'une huile végétale ou d'une graisse animale produisant respectivement l'ester méthylique d'un acide gras ou un acide gras. L'ester méthylique de l'acide gras peut ensuite être hydrolysé pour former l'acide gras. Ensuite, l'acide gras est transformé en nitrile par réaction avec l'ammoniac, et finalement en aminé par hydrogénation du nitrile ainsi obtenu.  Processes for producing nitriles and / or fatty amines from fatty acids extracted from vegetable or animal oils are known. This process is described in the Kirk-Othmer Encyclopedia Vol 2, 4 ° Edition, page 411. The fatty amine is obtained in several stages. The first step consists of methanolysis or hydrolysis of a vegetable oil or an animal fat respectively producing the methyl ester of a fatty acid or a fatty acid. The methyl ester of the fatty acid can then be hydrolysed to form the fatty acid. Then, the fatty acid is converted to nitrile by reaction with ammonia, and finally to amine by hydrogenation of the nitrile thus obtained.
L'évolution actuelle en matière environnementale conduit dans le domaine de la chimie à privilégier l'exploitation des matières premières naturelles provenant d'une source renouvelable. C'est la raison pour laquelle certains travaux de recherche-développement ont été repris pour élaborer sur le plan industriel des procédés utilisant des acides/esters gras comme matière première de fabrication de ces nitriles.  Current environmental trends in the field of chemistry favor the exploitation of natural raw materials from a renewable source. This is the reason why some research and development work has been resumed to elaborate industrially processes using fatty acids / esters as raw material for the manufacture of these nitriles.
L'invention porte sur un procédé de nitrilation de la fonction acide ou bien de la fonction ester, selon le réactif utilisé, éventuellement insaturé. Le schéma réactionnel de la synthèse des nitriles à partir d'un acide gras peut se résumer de la façon suivante : The invention relates to a method for the nitrilation of the acid function or the ester function, depending on the reagent used, optionally unsaturated. The reaction scheme for the synthesis of nitriles from a fatty acid can be summarized as follows:
R-COOH R-CONH2 R-CN + H20 R-COOH R-CONH 2 R-CN + H 2 O
H20 H 2 0
Acide Sel Amide Nitrile  Nitrile Amide Salt
Par nitrilation, on entend au sens de la présente invention une réaction entre un acide gras ou un ester d'acide gras et de l'ammoniac conduisant à la transformation, respectivement de la fonction C02H ou C02R en fonction CN. Cette réaction de nitrilation s'appelle également ammoniation, car cette réaction implique de l'ammoniac. For the purposes of the present invention, the term "nitrilation" means a reaction between a fatty acid or a fatty acid ester and ammonia leading to the conversion of the function C0 2 H or C0 2 R, respectively, in CN function. This nitrilation reaction is also called ammoniation because this reaction involves ammonia.
Il existe 2 types de procédés fondés sur ce schéma réactionnel : un procédé en phase liquide (en général en batch) et un procédé en phase vapeur (en général en continu).  There are 2 types of processes based on this reaction scheme: a liquid phase process (usually in batch) and a vapor phase process (usually continuous).
Dans le procédé batch en phase liquide, on charge l'acide gras ou un mélange d'acides gras avec un catalyseur, qui est généralement un oxyde métallique, et le plus fréquemment l'oxyde de zinc. On porte le milieu réactionnel jusqu'à environ 150°C sous agitation, puis on commence à introduire l'ammoniac gazeux. Dans un premier temps, on forme un sel d'ammonium ou savon d'ammonium. La température du milieu réactionnel est ensuite portée aux alentours de 250°C-300°C toujours sous introduction d'ammoniac. Le sel d'ammonium se transforme en amide avec libération d'une première molécule d'eau. Puis, dans un deuxième temps et avec l'aide du catalyseur, l'amide se transforme en nitrile avec formation d'une deuxième molécule d'eau. Cette eau formée est éliminée en continu du réacteur en entraînant l'ammoniac qui n'a pas réagi et un peu de chaînes grasses parmi les plus légères. Les procédés en phase liquide, utilisant des réacteurs batch, nécessitent des temps de réaction très longs, notamment de plusieurs heures. Dans le procédé en phase gaz (continu), la charge est vaporisée et amenée au contact avec de l ' ammoniac, dont la température est comprise entre 250°C et 600 °C, en présence d'un catalyseur. Ce catalyseur est en général choisi parmi la famille des oxydes métalliques constituée par les oxydes de métaux, pris seul ou en mélange, tels que Zr, Ta, Ga In, Se, Nb, Hf, Fe, Zn, Sn ou de l ' alumine, un oxyde de thorium, et notamment de l ' alumine dopée. Les procédés en phase gaz sont effectués en continu à une température de l'ordre de 300°C , et dans ces conditions les temps de contact sont de l ' ordre de quelques secondes sur le catalyseur. Néanmo ins, dès que la température diminue, avec les catalyseurs connus, les conversions chutent, et il est alors nécessaire d' augmenter le temps de contact moyen pour retrouver des conversions élevées . In the liquid phase batch process, the fatty acid or a mixture of fatty acids is charged with a catalyst, which is generally a metal oxide, and most frequently zinc oxide. The reaction medium is brought to about 150 ° C. with stirring, and ammonia gas is then introduced. First, an ammonium salt or ammonium soap is formed. The temperature of the reaction medium is then raised to around 250 ° C.-300 ° C., still under the introduction of ammonia. The ammonium salt is converted to amide with release of a first molecule of water. Then, in a second step and with the help of the catalyst, the amide is transformed into nitrile with formation of a second molecule of water. This formed water is continuously removed from the reactor by driving unreacted ammonia and some of the lighter fatty chains. Liquid phase processes, using batch reactors, require very long reaction times, especially several hours. In the gas phase (continuous) process, the feed is vaporized and brought into contact with ammonia, the temperature of which is between 250 ° C and 600 ° C, in the presence of a catalyst. This catalyst is generally chosen from the family of metal oxides consisting of metal oxides, taken alone or as a mixture, such as Zr, Ta, Ga In, Se, Nb, Hf, Fe, Zn, Sn or alumina. , an oxide of thorium, and in particular doped alumina. The gas phase processes are carried out continuously at a temperature of the order of 300 ° C., and under these conditions the contact times are of the order of a few seconds on the catalyst. However, as soon as the temperature decreases, with the known catalysts, the conversions fall, and it is then necessary to increase the average contact time to find high conversions.
Ces réactions, sous leurs différentes formes sont mentionnées dans les Encyclopédies Ullmann vol. A2, page 20 et Kirk Othmer vo l. 2 pages 41 1 -412 , et ont fait l'obj et de nombreux brevets déposés notamment par la société KAO . On peut citer les brevets US 6,005 , 134, 6,080, 891 et 7,259,274, qui décrivent la synthèse de nitriles aliphatiques en phase liquide à partir d'acides gras en présence d'un catalyseur au titane. Pour le même déposant et pour le même typ e de procédé, on peut relever les demandes j aponaises N° 1 1 - 1 17990 (26/04/ 1999) avec un catalyseur au niobium et N° 9-4965 ( 14/0 1 / 1997) avec un catalyseur au zirconium. On peut également citer un brevet US n° 4, 801 ,730 qui décrit la nitrilation des glycérides en phase liquide et une demande j aponaise au nom de Lion Corp du 13/03/ 199 1 (Publication N° JP 4283549) qui vise la synthèse de nitrile en phase gazeuse.  These reactions, in their different forms, are mentioned in the Ullmann Encyclopedias Vol. A2, page 20 and Kirk Othmer vo l. 2 pages 41 1-412, and have been the object of many patents filed in particular by the company KAO. US Pat. Nos. 6,005, 134, 6,080, 891 and 7,259,274, which describe the synthesis of liquid phase aliphatic nitriles from fatty acids in the presence of a titanium catalyst. For the same Applicant and for the same type of process, it is possible to note the French Applications Nos. 1 1 - 1 17990 (26/04/1999) with a niobium catalyst and No. 9-4965 (14/0 1 / 1997) with a zirconium catalyst. No. 4,801,730 which describes the nitrilation of glycerides in the liquid phase and a French application in the name of Lion Corp of 13/03/199 1 (Publication No. JP 4283549) which nitrile synthesis in the gas phase.
A l'o ccasion des travaux qu' elle a menés, la demanderesse a observé que l ' étape de nitrilation jouait un rôle important, notamment lorsqu ' elle était réalisée sur un acide ω-insaturé. En effet, la lo calisation de la double liaison en bout de chaîne et donc peu protégée, entraîne la formation d'isomères par suite du déplacement de la double liaison. Ayant observé ces phénomènes, elle a constaté, que cet inconvénient pouvait être largement limité en travaillant avec l'ester plutôt que l'acide correspondant ce qui permettait d 'opérer dans des conditions « plus douces » . En effet, le point d' ébullition de l'ester étant moins élevé que celui de l ' acide correspondant, il est possible d'atteindre des tensions de vapeur plus fortes avec l ' ester. En outre, en opérant dans un réacteur fonctionnant en continu, soit en phase gazeuse, soit en phase mixte liquide-gaz, le temps de séjour des réactifs au contact des catalyseurs étant nettement plus réduit qu'en phase liquide classique (batch) permet de limiter l ' isomérisation au cours du processus . At the time of the work she conducted, the Applicant observed that the nitrilation stage played an important role, especially when it was carried out on a ω-unsaturated acid. Indeed, the lo calization of the double bond at the end of the chain and therefore poorly protected, leads to the formation of isomers as a result of displacement of the double bond. Having observed these phenomena, she found that this disadvantage could be largely limited by working with the ester rather than the corresponding acid which made it possible to operate in "softer" conditions. Since the boiling point of the ester is lower than that of the corresponding acid, it is possible to reach higher vapor pressures with the ester. In addition, by operating in a reactor operating continuously, either in the gas phase or in the mixed liquid-gas phase, the residence time of the reactants in contact with the catalysts being much smaller than in the conventional liquid phase (batch) allows limit isomerization during the process.
Toutefois, il a été constaté que même en partant d'un ester, la réaction conduit à la formation d'isomères .  However, it has been found that even starting from an ester, the reaction leads to the formation of isomers.
Il est important de contrôler cette étape de nitrilation, et notamment lorsque l ' étape suivante est une étape de métathèse ou d' hydro formylation. En effet, celles-ci portent sur la transformation de la double liaison. Ainsi, lorsque la réaction de nitrilation conduit à la formation de plusieurs nitriles portant des doubles liaisons à des positions différentes sur la chaîne grasse, la réaction de métathèse ou d' hydro formylation conduira nécessairement à des sous-produits non désirés, résultants de cette réaction de métathèse ou d' hydro formylation sur les isomères du nitrile non souhaités . Par conséquent, pour ce type de synthèse, il est essentiel que la double liaison ne migre pas sur la chaîne carbonée.  It is important to control this nitrilation step, and especially when the next step is a metathesis or hydro formylation step. Indeed, these relate to the transformation of the double bond. Thus, when the nitrilation reaction results in the formation of several nitriles bearing double bonds at different positions on the fatty chain, the metathesis or hydro formylation reaction will necessarily lead to unwanted byproducts resulting from this reaction. metathesis or hydro formylation on undesired nitrile isomers. Therefore, for this type of synthesis, it is essential that the double bond does not migrate on the carbon chain.
De plus, il existe toujours le besoin de rechercher des conditions opératoires conduisant à un taux de conversion et un rendement meilleurs.  In addition, there is still the need to seek operating conditions leading to a better conversion rate and yield.
En effet, il a été observé que lorsque la température de la réaction diminuait, le taux d' amide, c ' est-à-dire le composé intermédiaire était plus important.  Indeed, it has been observed that when the temperature of the reaction decreased, the amide level, that is to say the intermediate compound was greater.
De même, il a été observé que lorsque le réactif est de l ' ester méthylique, il se formait de l ' amide N-méthylé en tant que composé intermédiaire, la formation de cet amide intermédiaire bloquant la nitrilation. De plus, cette impureté limite les applications potentielles des nitriles ainsi obtenus. Ainsi, il est recherché un procédé de nitrilation en phase gaz ou en phase mixte liquide-gaz plus performant, que le réactif soit un acide ou un ester, saturé ou insaturé. Le but recherché est l 'obtention d'un procédé conduisant à un excellent taux de conversion, avec un excellent rendement, en diminuant la teneur en sous-produits issus de la migration de la double liaison, lorsque le réactif utilisé est insaturé, en diminuant la teneur en sous-produits issus de la méthylation de l ' amide intermédiaire, lorsque le réactif utilisé est un ester méthylique, et de diminuer la teneur en amide intermédiaire. Similarly, it has been observed that when the reagent is methyl ester, N-methyl amide is formed as an intermediate compound, the formation of this intermediate amide blocking the nitrilation. In addition, this impurity limits the potential applications of the nitriles thus obtained. Thus, it is desired a more efficient nitrilation method in the gas phase or in the liquid-gas mixed phase, whether the reagent is an acid or an ester, saturated or unsaturated. The aim is to obtain a process leading to an excellent conversion rate, with an excellent yield, by reducing the content of by-products resulting from the migration of the double bond, when the reagent used is unsaturated, decreasing the by-product content resulting from the methylation of the intermediate amide, when the reagent used is a methyl ester, and to reduce the content of intermediate amide.
Enfin, il est recherché un procédé moins coûteux en termes d' énergie et de catalyseur mis en œuvre.  Finally, it is sought a less expensive method in terms of energy and catalyst implemented.
L 'invention a pour obj et un procédé de nitrilation d' acide gras ou d ' ester d' acide gras, éventuellement insaturé, par action de l ' ammoniac dans un réacteur fonctionnant en continu en phase gaz ou en phase mixte gaz-liquide dans une gamme de température allant de 1 80 à 400°C, en présence d'un catalyseur solide comportant :  The object of the invention is a process for the nitrilation of fatty acid or fatty acid ester, which may be unsaturated, by the action of ammonia in a reactor operating continuously in the gas phase or in the mixed gas - liquid phase in a reactor a temperature range of 1 80 to 400 ° C, in the presence of a solid catalyst comprising:
-au moins un oxyde métallique, dont le métal appartient à la co lonne 8 du tableau de la classification périodique en mélange avec at least one metal oxide, the metal of which belongs to column 8 of the periodic table in admixture with
-au moins un oxyde métallique choisi parmi les oxydes d' aluminium, les oxydes de zirconium, les oxydes de niobium, les oxydes de tantale et les oxydes d' étain, at least one metal oxide chosen from aluminum oxides, zirconium oxides, niobium oxides, tantalum oxides and tin oxides,
le ou les oxydes métalliques, dont le métal appartient à la co lonne 8 étant présent dans un rapport volumique de 0, 1 à 0,6 par rapport au volume du mélange de la totalité des oxydes métalliques.  the metal oxide or oxides, the metal of which belongs to column 8, being present in a volume ratio of 0.1 to 0.6 relative to the volume of the mixture of all the metal oxides.
En effet, il a été observé que l 'utilisation de ces catalyseurs particuliers conduisait à la nitrilation des réactifs dans un temps de contact moyen extrêmement court. Par exemple, la nitrilation de 1 ,6 g/h d' acide laurique pour un lit de 1 ,5 ml (~ l -2g de catalyseur) d' ammoniac s ' est effectuée en 4,5 secondes pour des températures allant de 200°C à 300°C . Cette cinétique est à mettre en parallèle avec les 8 à 10 heures nécessaires à la nitrilation en phase liquide en réacteur batch. Cette cinétique obtenue à une température relativement basse est surprenante, ainsi que le rendement et la conversion de cette réaction de nitrilation dans de telles conditions opératoires. De plus, il a été observé, l ' absence d' isomérisation de la double liaison lors de la réaction de nitrilation de l 'undécènoate de méthyle, pendant un temps de contact court et à des températures relativement basses. Il semblerait que la double liaison n' ait pas le temps ou l ' énergie nécessaire pour migrer le long de la chaîne carbonée de l ' acide ou de l ' ester. Indeed, it has been observed that the use of these particular catalysts led to the nitrilation of the reactants in an extremely short average contact time. For example, the nitrilation of 1, 6 g / h of lauric acid for a bed of 1.5 ml (~ 1 -2 g of catalyst) of ammonia was effected in 4.5 seconds for temperatures of 200 ° C at 300 ° C. This kinetics is to be compared with the 8 to 10 hours required for liquid phase nitrilation in a batch reactor. This kinetics obtained at a relatively low temperature is surprising, as well as the yield and the conversion of this nitrilation reaction under such operating conditions. In addition, the absence of isomerization of the double bond during the nitrilation reaction of methyl undecenoate has been observed during a short contact time and at relatively low temperatures. It would seem that the double bond does not have the time or energy to migrate along the carbon chain of the acid or ester.
Enfin, il a été observé les rendements bien meilleurs pour cette réaction de nitrilation, par exemple pour le couple oxyde de fer et oxyde de zircone que pour la zircone seule, aussi bien à 200°C qu' à 250°C . Le mélange Fe203/Zr02 étant beaucoup moins cher que la zircone seule, ce résultat montre que le procédé est économiquement intéressant. Finally, much better yields have been observed for this nitrilation reaction, for example for the iron oxide and zirconia oxide pair than for the zirconia alone, both at 200 ° C. and at 250 ° C. Since the Fe 2 O 3 / ZrO 2 mixture is much less expensive than zirconia alone, this result shows that the process is economically interesting.
L 'invention porte également sur un catalyseur so lide comportant au moins un oxyde métallique, dont le métal appartient à la co lonne 8 du tableau de la classification périodique en mélange avec au moins un oxyde métallique choisi parmi les oxydes d' aluminium, les oxydes de zirconium, les oxydes de niobium, les oxydes de tantale et les oxydes d' étain, le ou les oxydes métalliques, dont le métal appartient à la co lonne 8 étant présent dans un rapport volumique de 0, 1 à 0,6 par rapport au volume du mélange de la totalité des oxydes métalliques.  The invention also relates to a solid catalyst comprising at least one metal oxide, the metal of which belongs to column 8 of the periodic table in admixture with at least one metal oxide chosen from aluminum oxides, oxides and of zirconium, niobium oxides, tantalum oxides and tin oxides, the metal oxide or oxides, the metal of which belongs to column 8 being present in a volume ratio of 0.1 to 0.6 relative to to the volume of the mixture of all the metal oxides.
L 'invention porte sur le procédé de préparation de ce catalyseur, ainsi que l 'utilisation de ce catalyseur dans des procédés de nitrilation.  The invention relates to the process for the preparation of this catalyst as well as the use of this catalyst in nitrilation processes.
D ' autres caractéristiques, aspects, objets et avantages de la présente invention apparaîtront encore plus clairement à la lecture de la description et des exemp les qui suivent .  Other features, aspects, objects and advantages of the present invention will become more apparent upon reading the description and the following examples.
D'autre part, tout intervalle de valeurs désigné par l'expression " entre a et b" représente le domaine de valeurs allant de plus de a à moins de b (c ' est-à-dire bornes a et b exclues), tandis que tout intervalle de valeurs désigné par l'expression " de a à b" signifie le domaine de valeurs allant de a jusqu'à b (c ' est-à-dire incluant les bornes strictes a et b) . Par phase mixte gaz-liquide, on entend au sens de la présente invention, un procédé mettant en œuvre un fluide mixte gaz-liquide incluant un liquide en tant que phase continue et un gaz en tant que phase dispersée ou bien un liquide en tant que phase dispersée et un gaz en tant que phase continue. Dans un mode de liquide descendant sur un catalyseur en lit fixe, on a une configuration de lit ruisselant, dans un mo de de liquide montant et catalyseur en lit fixe, on a une configuration en lit immergé. Le réacteur peut aussi fonctionner en mode lit fluidisé. Dans cette configuration, le catalyseur est maintenu fluidisé non seulement par le flux de gaz, mais aussi par la vaporisation de la charge liquide qui génère ainsi un grand vo lume de gaz. On the other hand, any range of values designated by the expression "between a and b" represents the range of values from more than a to less than b (i.e., excluding terminals a and b), while that any range of values designated by the expression "from a to b" means the range of values from a to b (that is, including the strict limits a and b). For the purposes of the present invention, the term "gas-liquid mixed phase" is intended to mean a process employing a mixed gas-liquid fluid including a liquid as a continuous phase and a gas as a dispersed phase or a liquid as a dispersed phase and a gas as a continuous phase. In a liquid downflow mode on a fixed bed catalyst, there is a trickle bed configuration, in a rising bed of liquid and fixed bed catalyst, it has a submerged bed configuration. The reactor can also operate in fluidized bed mode. In this configuration, the catalyst is maintained fluidized not only by the gas flow, but also by the vaporization of the liquid charge which thus generates a large volume of gas.
Procédé de nitrilation  Process of nitrilation
L 'invention porte sur un procédé de nitrilation d' acide gras ou d' ester d' acide gras, éventuellement insaturé, par action de l ' ammoniac dans un réacteur fonctionnant en continu en phase gaz ou en phase mixte gaz-liquide dans une gamme de température allant de 1 80 à 400°C en présence d'un catalyseur solide comportant au moins un oxyde métallique, dont le métal appartient à la colonne 8 du tableau de la classification périodique en mélange avec au moins un oxyde métallique choisi parmi les oxydes d' aluminium, les oxydes de zirconium, les oxydes de niobium, les oxydes de tantale et les oxydes d' étain, le ou les oxydes métalliques, dont le métal appartient à la co lonne 8 étant présent dans un rapport volumique de 0, 1 à 0,6 par rapport au volume du mélange de la totalité des oxydes.  The invention relates to a method for the nitrilation of fatty acid or fatty acid ester, optionally unsaturated, by the action of ammonia in a reactor operating continuously in the gas phase or in the mixed gas - liquid phase in a range. temperature ranging from 1 80 to 400 ° C in the presence of a solid catalyst comprising at least one metal oxide, the metal of which belongs to column 8 of the periodic table in admixture with at least one metal oxide chosen from oxides of aluminum, zirconium oxides, niobium oxides, tantalum oxides and tin oxides, the metal oxide or oxides, the metal of which belongs to column 8 being present in a volume ratio of 0.1 at 0.6 relative to the volume of the mixture of all the oxides.
Les réactifs du procédé de nitrilation selon l' invention peuvent être des acides ou des esters gras, éventuellement insaturés, de préférence ω-insaturés.  The reagents of the nitrilation process according to the invention may be fatty acids or esters, optionally unsaturated, preferably ω-unsaturated.
Par « gras » au sens de la présente invention, on entend un acide ou un ester comprenant une chaîne carbonée, saturée ou insaturée, linéaire comportant de 8 à 36 atomes de carbone. De préférence, les acides et esters utiles pour le procédé de l ' invention sont de formule suivante :  For the purposes of the present invention, the term "fatty" is understood to mean an acid or an ester comprising a carbon chain, saturated or unsaturated, linear having from 8 to 36 carbon atoms. Preferably, the acids and esters which are useful for the process of the invention are of the following formula:
CH2=CH-(CH2)„-COOR dans laquelle CH 2 = CH- (CH 2 ) "- COOR in which
n représente l ' entier 7 ou 8 et  n represents the integer 7 or 8 and
R représente soit un atome d' hydrogène, soit un radical alkyle comportant 1 à 4 atomes de carbone.  R represents either a hydrogen atom or an alkyl radical having 1 to 4 carbon atoms.
De préférence, le procédé de l ' invention utilise comme charge des acides ou des esters ω-insaturés comportant soit 1 0 atomes, soit 1 1 atomes de carbone par mo lécule. Les premiers, notamment le 9- décénoate de méthyle sont commercialisés sous forme d' ester par la société ELEVANCE Renewable Sciences . Les seconds, notamment le 10-undécénoate de méthyle sont fabriqués par la société ARKEMA dans le cadre de son procédé à base d' huile de ricin, l'undécylénate de méthyle étant obtenu après pyrolyse.  Preferably, the process of the invention uses as acids ou-unsaturated acids or esters having either 10 atoms or 1 carbon atoms per molecule. The former, in particular methyl 9-decenoate, are marketed in the form of esters by ELEVANCE Renewable Sciences. The latter, in particular methyl 10-undecenoate, are manufactured by the company Arkema as part of its castor oil-based process, the methyl undecylenate being obtained after pyrolysis.
L'étape de nitrilation est réalisée dans un réacteur fonctionnant en continu, c ' est-à-dire dans lequel les réactifs qu' ils soient à l ' origine gazeux, solides ou liquides sont introduits (et les produits extraits) dans le réacteur en continu selon des débits prédéterminés.  The nitrilation step is carried out in a reactor operating continuously, that is to say in which the reactants that are initially gaseous, solid or liquid are introduced (and the extracted products) into the reactor. continuous according to predetermined rates.
Le procédé de nitrilation des acides gras et les esters est conduit à une température de réaction allant de 1 80 à 400 °C, et de préférence de 200 à 300 °C et de manière plus préférée de 200 à 250 °C . La charge des acides ou des esters gras, éventuellement insaturés est vaporisée et amenée à une température allant de 1 80 à 350 °C au contact avec l ' ammoniac, dont la température d ' introduction va de 150 à 600 °C .  The method of nitrilating fatty acids and esters is conducted at a reaction temperature of from 180 to 400 ° C, and preferably from 200 to 300 ° C and more preferably from 200 to 250 ° C. The charge of fatty acids or fatty esters, optionally unsaturated, is vaporized and brought to a temperature ranging from 180 ° to 350 ° C. in contact with ammonia, the introduction temperature of which is 150 ° to 600 ° C.
La pression exercée dans le réacteur peut aller de 0, 1 à 1 0 atmosphères (absolues), et de préférence de 0,5 à 5 atm, et de manière encore plus préférée de 1 à 3 atm.  The pressure exerted in the reactor can range from 0.1 to 10 atmospheres (absolute), and preferably from 0.5 to 5 atm, and even more preferably from 1 to 3 atm.
Le ratio mo laire NH3/ester gras ou NH3/acide gras des réactifs peut aller de 1 à 50, de préférence de 3 à 30, et de manière encore plus préférée de 5 à 20. The molar ratio NH 3 / fatty ester or NH 3 / fatty acid of the reactants may range from 1 to 50, preferably from 3 to 30, and even more preferably from 5 to 20.
En phase gazeuse pure  In pure gaseous phase
Dans un premier mode de réalisation, les deux réactifs peuvent être introduits dans le réacteur à l ' état gazeux (phase gazeuse pure) .  In a first embodiment, the two reagents can be introduced into the reactor in the gaseous state (pure gaseous phase).
L ' acide ou l ' ester d' acides gras, éventuellement insaturé est vaporisé et amené à une température allant de 1 80 à 350°C au contact avec l ' ammoniac, dont la température d' introduction va de 150 à 600°C et sous une pression allant de 0, 1 à 10 atmosphères (absolues), de préférence de 0,5 à 5 atmosphères et de manière encore plus préférée de 1 à 3 atmosphères. The fatty acid or ester, optionally unsaturated, is vaporized and brought to a temperature ranging from 1 80 to 350 ° C in contact with with ammonia, whose introduction temperature is from 150 to 600 ° C. and at a pressure ranging from 0.1 to 10 atmospheres (absolute), preferably from 0.5 to 5 atmospheres and even more preferably from 1 to 3 atmospheres.
Les débits d'introduction des réactifs sont tels que le temps de contact avec le catalyseur so lide va de 1 seconde à 300 secondes . Dans ce cas, le temps de contact est déterminé par le ratio calculé comme suit : {volume de catalyseur (en litres) x 3600 } / { [débit de l ' ester ou de l ' acide(en mo les/h) + débit d' ammoniac (en mo les/h)] x 22,4 } =temps de contact en secondes.  The rates of introduction of the reagents are such that the contact time with the solid catalyst ranges from 1 second to 300 seconds. In this case, the contact time is determined by the ratio calculated as follows: (catalyst volume (in liters) x 3600} / {[flow of the ester or acid (in mo / hr) + flow rate Ammonia (in Mo / h)] x 22.4} = contact time in seconds.
En phase mixte  In mixed phase
De préférence, le procédé de nitrilation en phase mixte est mis en œuvre avec les acides gras .  Preferably, the mixed phase nitrilation process is carried out with the fatty acids.
Dans l ' autre mode de réalisation (phase mixte), l' ammoniac est introduit sous forme de gaz, alors que l' acide est introduit, après un préchauffage éventuel, dans le réacteur à proximité du lit catalytique, au moins en partie sous forme liquide à un débit déterminé pour s ' écouler sous forme d'un film (lit ruisselant) sur le lit catalytique chauffé au contact duquel une fraction du liquide est vaporisée . La réaction ou la série de réactions s ' effectue(nt) au contact de la surface du catalyseur ou dans sa proximité immédiate . Cette technique dit du « lit ruisselant » est bien connue et largement employée dans l' industrie pétrolière. Le flux d' ammoniac peut être co-courant ou à contre-courant du flux de l ' acide.  In the other embodiment (mixed phase), the ammonia is introduced in the form of a gas, whereas the acid is introduced, after possible preheating, into the reactor near the catalytic bed, at least partly in the form of a gas. liquid at a rate determined to flow in the form of a film (dripping bed) on the heated catalyst bed in contact with which a fraction of the liquid is vaporized. The reaction or series of reactions is carried out in contact with the catalyst surface or in its immediate vicinity. This so - called "trickling bed" technique is well known and widely used in the oil industry. The ammonia stream can be co-current or countercurrent to the flow of the acid.
Le débit d'introduction de l ' acide est tel que le temps de contact moyen de la phase liquide dans le réacteur est inférieur à 1 heure, et de préférence inférieur à 30 minutes. Ce temps de contact est déterminé par le calcul suivant : vo lume de catalyseur (en litres)/débit de l ' acide (en litres liquides à 25 °C par heure), soit l ' inverse de la vitesse vo lumique liquide horaire liquide.  The rate of introduction of the acid is such that the average contact time of the liquid phase in the reactor is less than 1 hour, and preferably less than 30 minutes. This contact time is determined by the following calculation: volume of catalyst (in liters) / flow rate of the acid (in liquid liters at 25 ° C. per hour), ie the inverse of the hourly liquid liquid hourly velocity.
Dans ce mode de mise en œuvre, on peut travailler à co- courant, c'est-à-dire le courant gazeux et le flux liquide sont descendants, ou à contre-courant, le flux gazeux étant ascendant et le courant liquide descendant. Cette dernière variante est préférée dans le procédé de l'invention. La version contre-courant, gaz montant et acide descendant, peut être particulièrement intéressante pour limiter l 'hydro lyse du nitrile formé. En effet dans cette configuration, l ' ammoniac est inj ecté en pied, l ' eau et l ' alcool sortent en tête, l ' acide entre en tête et le nitrile sort en pied. Donc en pied, on a une forte concentration en nitrile et en ammoniac et en tête une forte concentration en eau et alcool, et moindre en ammoniac. On peut donc déplacer les équilibres, notamment celui de l ' hydrolyse du nitrile qui redonne de l ' acide. In this mode of implementation, it is possible to work in co-current, that is to say the gaseous stream and the liquid flow are descending, or in countercurrent, the gaseous flow being ascending and the liquid flow descending. This last variant is preferred in the method of the invention. The countercurrent version, rising gas and descending acid, may be particularly advantageous for limiting the hydrolysis of the formed nitrile. In this configuration, the ammonia is injected in the foot, the water and the alcohol come out at the head, the acid enters the head and the nitrile comes out in the foot. So in the foot, it has a high concentration of nitrile and ammonia and at the head a high concentration of water and alcohol, and less ammonia. The equilibrium can thus be displaced, in particular that of the hydrolysis of the nitrile which gives back acid.
Catalyseur  Catalyst
La présente invention a également pour objet un catalyseur so lide.  The present invention also relates to a solid catalyst.
Le catalyseur so lide selon la présente invention comprend The solid catalyst according to the present invention comprises
-au moins un oxyde métallique, dont le métal appartient à la co lonne 8 du tableau de la classification périodique en mélange avecat least one metal oxide, the metal of which belongs to column 8 of the periodic table in admixture with
-au moins un oxyde métallique choisi parmi les oxydes d' aluminium, les oxydes de zirconium, les oxydes de niobium, les oxydes de tantale et les oxydes d' étain, at least one metal oxide chosen from aluminum oxides, zirconium oxides, niobium oxides, tantalum oxides and tin oxides,
le ou les oxydes métalliques, dont le métal appartient à la co lonne 8 étant présent dans un rapport volumique de 0, 1 à 0,6 par rapport au volume du mélange de la totalité des oxydes métalliques.  the metal oxide or oxides, the metal of which belongs to column 8, being present in a volume ratio of 0.1 to 0.6 relative to the volume of the mixture of all the metal oxides.
De préférence, l'oxyde métallique, dont le métal appartient à la co lonne 8 du tableau de la classification périodique est un oxyde de fer. Il est notamment choisi parmi FeO, Fe3C" 4 et Fe203. L 'oxyde métallique dont le métal appartient à la colonne 8 du tableau de la classification périodique préféré est l 'oxyde ferrique : Fe203. Preferably, the metal oxide, the metal of which belongs to column 8 of the Periodic Table, is an iron oxide. It is especially chosen from FeO, Fe 3 C 4 and Fe 2 O 3. The metal oxide whose metal belongs to column 8 of the table of the preferred periodic table is ferric oxide: Fe 2 O 3 .
De préférence, les oxydes métalliques choisis parmi les oxydes d' aluminium, les oxydes de zirconium, les oxydes de niobium, les oxydes de tantale et les oxydes d' étain sont choisis parmi les oxydes d' aluminium, les oxydes de zirconium et les oxydes de niobium. Plus particulièrement, ils sont choisis parmi l ' oxyde d' aluminium : A1203 , l'oxyde de zirconium Zr02, et le pentoxyde de niobium : Nb205. Preferably, the metal oxides chosen from aluminum oxides, zirconium oxides, niobium oxides, tantalum oxides and tin oxides are chosen from aluminum oxides, zirconium oxides and oxides. of niobium. More particularly, they are chosen from aluminum oxide: Al 2 O 3 , zirconium oxide ZrO 2 , and niobium pentoxide: Nb 2 O 5 .
Certains de ces oxydes existent sous certaines formes cristallographiques . De préférence, l ' alumine utilisée est l' alumine gamma commercialisée par la société BASF sous la référence commerciale AL-3996, ou encore par les sociétés Axens et Saso l. Some of these oxides exist in certain crystallographic forms. Preferably, the alumina used is alumina gamma marketed by the company BASF under the commercial reference AL-3996, or by the companies Axens and Saso l.
La zircone (Zr02) utilisée est commercialisée par les sociétés Norpro-StGobain, Daiichi Kigenso KK, et MEL, l' oxyde de Niobium (Nb205) est commercialisé par les sociétés STARCK et CBMM, et l'oxyde de fer III hydraté est commercialisé entre autres par la société Sigma-Aldrich (FeO(OH)) (catalyst grade, 30-50 mesh cassé et tamisé) . The zirconia (ZrO 2 ) used is sold by the companies Norpro-StGobain, Daiichi Kigenso KK, and MEL, Niobium oxide (Nb 2 0 5 ) is marketed by the companies STARCK and CBMM, and iron oxide III hydrated is marketed among others by Sigma-Aldrich (FeO (OH)) (catalyst grade, 30-50 mesh broken and sieved).
De préférence, le catalyseur so lide selon l' invention comporte les combinaisons suivantes : l'oxyde ferrique : Fe203 sur un support pentoxyde de niobium : Nb205 ; l'oxyde ferrique : Fe203 sur un support oxyde d ' aluminium : A1203 et ainsi que l'oxyde ferrique : Fe203 sur un support oxyde de zirconium : Zr02. Preferably, the solid catalyst according to the invention comprises the following combinations: ferric oxide: Fe 2 O 3 on a niobium pentoxide support: Nb 2 0 5 ; ferric oxide: Fe 2 O 3 on an aluminum oxide support: Al 2 O 3 and ferric oxide: Fe 2 O 3 on a zirconium oxide support: Zr0 2 .
Le rapport volumique de l'oxyde métallique, dont le métal appartient à la co lonne 8 du tableau de la classification périodique sur le vo lume du mélange de la totalité des oxydes va de 0, 1 à 0,6.  The volume ratio of the metal oxide, the metal of which belongs to column 8 of the table of the periodic table on the volume of the mixture of all the oxides, ranges from 0.1 to 0.6.
De préférence, le ratio vo lumique du couple oxyde de fer/oxyde d' alumine va de 0,2 à 0,5.  Preferably, the volumetric ratio of the iron oxide / alumina oxide pair is from 0.2 to 0.5.
De préférence, le ratio vo lumique du couple oxyde de fer/oxyde de zirconium va de 0,2 à 0,5.  Preferably, the volumetric ratio of the iron oxide / zirconium oxide pair ranges from 0.2 to 0.5.
De préférence, le ratio vo lumique du couple oxyde de fer/oxyde de niobium va de 0,2 à 0,5 , notamment de 0,25 à 0,4.  Preferably, the volumetric ratio of the iron oxide / niobium oxide pair ranges from 0.2 to 0.5, especially from 0.25 to 0.4.
De préférence, le catalyseur selon la présente invention se caractérise par une surface spécifique allant de 10 à 500m2/g, et de préférence de 40 à 300m2/g, plus préférentiellement de 40 à 250 m2/g, et notamment de40 à 200 m2/g. Par surface spécifique BET (Brunauer, Emmett et Teller), on entend la surface disponible par gramme de matière. Cette mesure est basée sur une adsorption de gaz à la surface du so lide étudié. La mesure de la surface spécifique est effectuée selon la norme ASTM D 3663 -84. Preferably, the catalyst according to the present invention is characterized by a specific surface area ranging from 10 to 500 m 2 / g, and preferably from 40 to 300 m 2 / g, more preferably from 40 to 250 m 2 / g, and in particular from 40 to 250 m 2 / g. 200 m 2 / g. BET specific surface area (Brunauer, Emmett and Teller) means the available surface area per gram of material. This measurement is based on a gas adsorption on the surface of the solids studied. The measurement of the specific surface area is carried out according to ASTM D 3663-84.
De préférence, le catalyseur est caractérisé par une distribution de taille des pores, telle que moins de 20 % du vo lume poreux soit dans des pores de diamètre inférieur à 2 nm, et de préférence inférieur à 3.5 nm, et de manière encore plus préférée inférieur à 7 nm. Les tailles des pores étant calculées selon les méthodes ASTM D4222-83 (par adsorption d'Azote) pour la mesure de distribution des vo lumes poreux et ASTM D4641 -87 pour le calcul des distributions de taille des pores. Preferably, the catalyst is characterized by a pore size distribution, such that less than 20% of the porous volume is in pores with a diameter of less than 2 nm, and preferably less than 3.5 nm, and even more preferably less than 7 nm. The pore sizes being calculated according to ASTM D4222-83 (Nitrogen adsorption) for porous void distribution measurement and ASTM D4641 -87 for calculating pore size distributions.
Le catalyseur peut se présenter sous forme de billes, d' extrudés, de pastilles, de forme cylindrique, ou polylobique, ou encore sous forme de cylindre creux avec un ou plusieurs trous, ou encore sous la forme de cylindre ayant des encoches le long des arêtes, ceci de manière à augmenter le ratio de surface externe du grain par rapport au volume du grain. Ce critère est important pour réduire les limitations diffusionnelles.  The catalyst may be in the form of beads, extrudates, pellets, cylindrical, or polylobic, or in the form of a hollow cylinder with one or more holes, or in the form of a cylinder having notches along them. edges, so as to increase the outer surface ratio of the grain relative to the volume of the grain. This criterion is important to reduce diffusional limitations.
De préférence, pour une catalyse sur un lit fixe, les grains ont une taille de 1 à 8 mm, et de préférence de 3 à 5 mm dans leur utilisation industrielle, dimension selon leur plus grande longueur.  Preferably, for catalysis on a fixed bed, the grains have a size of 1 to 8 mm, and preferably 3 to 5 mm in their industrial use, dimension along their greatest length.
De préférence, pour une catalyse sur un lit fluidisé, les grains ont une taille moyenne de 40 à 300 μιη, et de préférence de 80 à 1 50 μιη dans leur utilisation industrielle, les catalyseurs se présentent de préférence sous la forme de microbilles.  Preferably, for a catalysis on a fluidized bed, the grains have an average size of 40 to 300 μιη, and preferably 80 to 150 μιη in their industrial use, the catalysts are preferably in the form of microbeads.
Procédé de préparation du catalyseur  Process for preparing the catalyst
Comme méthode de préparation des catalyseurs, plusieurs méthodes peuvent convenir : la coprécipitation d'un sel ou d'un mélange de sel ; le malaxage de précurseurs en général sous forme de sels, d' oxydes ou hydroxydes ; l' imprégnation d'un composé par un autre, par exemple l ' imprégnation des oxydes d' aluminium, de zirconium ou de niobium par une solution contenant un précurseur d' oxyde de fer ; le broyage réactif, dans lequel les deux oxydes sont intimement mélangés par un broyage énergique, qui conduit à la formation d'un nouveau composé ; ou encore l ' atomisation. Les précurseurs des oxydes sous différentes formes peuvent être utilisés notamment sous forme oxyde, nitrate, carbonate, chlorure, sulfate (y compris oxysulfate), phosphate, composé organométallique, acétate, acétylacétonate. En l 'occurrence, la préparation d'un catalyseur à partir de l 'oxysulfate de zirconium conduit à un catalyseur convenable pour le procédé de l ' invention. Le mélange des oxydes métalliques selon la présente invention est de préférence un mélange mécanique. As a method of preparing the catalysts, several methods may be suitable: the coprecipitation of a salt or a mixture of salt; kneading precursors in general in the form of salts, oxides or hydroxides; impregnating a compound with another, for example impregnating aluminum, zirconium or niobium oxides with a solution containing an iron oxide precursor; reactive grinding, in which the two oxides are intimately mixed by vigorous grinding, which leads to the formation of a new compound; or atomization. The precursors of the oxides in different forms can be used in particular in oxide, nitrate, carbonate, chloride, sulfate (including oxysulfate), phosphate, organometallic compound, acetate, acetylacetonate. In this case, the preparation of a catalyst from zirconium oxysulphate results in a suitable catalyst for the process of the invention. The mixture of metal oxides according to the present invention is preferably a mechanical mixture.
Selon un mode de réalisation de l 'invention, les oxydes peuvent être séparément broyés, finement, de préférence de manière à atteindre des tailles de particules allant de 1 à 8 mm selon leur plus grande longueur, puis des vo lumes mesurés sont mélangés et homogénéisés .  According to one embodiment of the invention, the oxides can be separately ground finely, preferably so as to reach particle sizes ranging from 1 to 8 mm along their greatest length, then measured volumes are mixed and homogenized .
L 'invention vise enfin l 'utilisation du catalyseur tel que défini ci-dessus dans un procédé de nitrilation d' acides gras ou d' esters d' acide gras .  The invention finally relates to the use of the catalyst as defined above in a process for the nitrilation of fatty acids or of fatty acid esters.
Les exemples suivants servent à illustrer l' invention sans toutefois présenter un caractère limitatif.  The following examples serve to illustrate the invention without however being limiting in nature.
EXEMPLES EXAMPLES
Les catalyseurs utilisés dans les exemples présentent caractéristiques suivantes, figurant dans le tableau 1 ci-dessous : The catalysts used in the examples have the following characteristics, shown in Table 1 below:
Tableau 1 EXEMPLE 1 : Test sur l' ester méthylique de l ' acide laurique.  EXAMPLE 1: Test on the methyl ester of lauric acid.
Des tests ont été menés sur l ' ester méthylique de l ' acide laurique. Tests have been conducted on the methyl ester of lauric acid.
Mode opératoire :  Operating mode:
Le montage est constitué d'une chambre d' évaporation, où est alimenté continûment l ' ester dans son état liquide via une pompe péristaltique. Un flux contrôlé d' azote sec vient entraîner l ' ester et le transporte vers le lit catalytique en contrebas. Le flux contrôlé d' ammoniac vient rencontrer le flux d' ester+azote à l ' affleurement du lit catalytique qui est un cylindre de 8 mm de diamètre par 30 mm retenu sur un frité en inox. Le flux sortant est condensé une première fois à 150- 170°C afin de récupérer les lauriques (nitriles, amide, acide, méthylamide..), et une seconde fois à 12°C puis -77°C (via un piège à carboglace) pour condenser les légers . Le condensât est prélevé et analysé par GC-FID et GC-MS , à partir de quoi les concentrations en ester, nitrile et éventuellement amide et N-méthyl amide sont calculées. The assembly consists of an evaporation chamber, where the ester is fed continuously in its liquid state via a peristaltic pump. A controlled flow of dry nitrogen leads to the ester and the transports to the catalytic bed below. The controlled flow of ammonia comes to meet the flow of ester + nitrogen at the outcropping of the catalytic bed which is a cylinder of 8 mm diameter by 30 mm retained on a stainless steel frit. The outflow is condensed a first time at 150-170 ° C to recover the lauric (nitriles, amide, acid, methylamide ..), and a second time at 12 ° C and then -77 ° C (via a dry ice trap) ) to condense the light ones. The condensate is removed and analyzed by GC-FID and GC-MS, from which the ester, nitrile and optionally amide and N-methyl amide concentrations are calculated.
Les oxydes métalliques ont été séparément broyés finement puis des vo lumes mesurés ont été mis en commun et homogénéisés.  The metal oxides were separately finely ground and measured volumes were pooled and homogenized.
Résultats : Results:
1 . Avec le catalyseur Fe?_Oi et AbC 1. With the catalyst Fe? _Oi and AbC
Cette expérience a été menée avec 3 catalyseurs différents : de l ' alumine seule : A1203 , de l 'oxyde de fer seul : Fe203 et un mélange A120 et Fe203 dans un ratio vo lumique Fe203/(A1203 + Fe203) de 0.5. This experiment was carried out with 3 different catalysts: alumina alone: Al 2 O 3 , iron oxide alone: Fe 2 O 3 and a mixture Al 2 0 and Fe 2 O 3 in a volumetric ratio Fe 2 0 3 / (A1 2 0 3 + Fe 2 O 3 ) of 0.5.
Le temps de séjour moyen est de 4 ,5 secondes. Les résultats en termes de conversion, de nitrilation et relatif à la formation du sous- produit N-méthylé, chacun exprimé en pourcentage molaire figurent dans les tableaux ci-dessous. The average residence time is 4.5 seconds. The results in terms of conversion, nitrilation and relative to the formation of the N-methylated by-product, each expressed in molar percentage are shown in the tables below.
1.1 A 200°C 1.1 At 200 ° C
Tableau 2  Table 2
Il est constaté que, même à 200°C, qui est une température relativement basse, le mélange de catalyseurs selon l'invention conduit à une augmentation pour la nitrilation de 71% calculé par rapport à la valeur obtenue pour l'alumine seule et de 211%> calculé par rapport à la valeur obtenue pour l'oxyde de fer seul. D'autre part, il n'y a pas de formation d'amide N-méthylé. It is found that even at 200 ° C., which is a relatively low temperature, the catalyst mixture according to the invention leads to an increase for the nitrilation of 71% calculated with respect to the value obtained for the alumina alone and 211%> calculated with respect to the value obtained for iron oxide alone. On the other hand, there is no formation of N-methylated amide.
De plus, comparé aux résultats obtenus pour l'alumine seule, on constate que l'écart obtenu entre la teneur en conversion et celle en nitrilation est nettement plus faible, indiquant ainsi la faible teneur en sous-produits obtenue avec le catalyseur selon l'invention.  In addition, compared to the results obtained for alumina alone, it is found that the difference obtained between the conversion content and that in nitrilation is significantly lower, thus indicating the low content of by-products obtained with the catalyst according to the invention. invention.
1.2 A 250°C 1.2 at 250 ° C
Les résultats figurent dans le tableau 3 ci-dessous et en figureThe results are shown in Table 3 below and in Figure
1. 1.
Tableau 3  Table 3
Ces résultats montrent une nette amélioration de la teneur en conversion et en nitrilation pour le catalyseur selon l' invention comparé aux catalyseurs seuls . These results show a clear improvement in the conversion and nitrilation content for the catalyst according to the invention compared to catalysts alone.
Par conséquent, pour ce temps de séjour très court, on conserve la tendance obtenue à 200°C , à savoir de bons résultats en termes de conversion et de nitrilation avec une très faible différence entre ces deux valeurs, indiquant une faible teneur en sous-produits . La formation d ' amide N-méthyl est limitée, et est plus faible pour le mélange d' oxydes métalliques que pour les composés purs.  Therefore, for this very short residence time, the trend obtained at 200 ° C is maintained, namely good results in terms of conversion and nitrilation with a very small difference between these two values, indicating a low content of products. The formation of N-methyl amide is limited, and is lower for the metal oxide mixture than for the pure compounds.
Enfin, la figure 1 apporte la preuve de l' effet attendu lié aux valeurs du ratio volumique selon l' invention.  Finally, FIG. 1 provides the proof of the expected effect related to the values of the volume ratio according to the invention.
2 Avec le catalyseur Fe^Oj et ZrO? 2 With the catalyst Fe ^ O j and ZrO?
Cette expérience a été menée avec 3 catalyseurs différents : de la zircone seule : Zr02, de l 'oxyde de fer seul : Fe203 et un mélange Zr02 et Fe203 dans un ratio vo lumique Fe203/(Zr02 + Fe203) de 0.5. This experiment was carried out with 3 different catalysts: zirconia alone: Zr0 2 , iron oxide alone: Fe 2 0 3 and a mixture Zr0 2 and Fe 2 0 3 in a voluminal ratio Fe 2 0 3 / (Zr0 2 + Fe 2 O 3 ) of 0.5.
Le temps de séjour moyen est de 4 ,5 secondes. Les résultats en termes de conversion, de nitrilation, chacun exprimé en pourcentage mo laire figurent dans les tableaux ci-dessous . 2. 1 A 200°C The average residence time is 4.5 seconds. The results in terms of conversion, of nitrilation, each expressed as a percentage of metals are shown in the tables below. 2. At 200 ° C.
Les résultats figurent dans le tableau 4 ci-dessous. The results are shown in Table 4 below.
Tableau 4  Table 4
Il est constaté que le mélange de catalyseurs selon l 'invention conduit à une augmentation pour la nitrilation comparé aux oxydes métalliques utilisés seuls. It is found that the catalyst mixture according to the invention leads to an increase for the nitrilation compared to the metal oxides used alone.
2.2 A 250°C 2.2 at 250 ° C
Les résultats figurent dans le tableau 5 ci-dessous et en figureThe results are shown in Table 5 below and in Figure
2. 2.
Tableau 5  Table 5
Ces résultats montrent une nette amélioration de la teneur en conversion et en nitrilation pour le catalyseur selon l' invention comparé aux catalyseurs seuls . These results show a clear improvement in the conversion and nitrilation content for the catalyst according to the invention compared to catalysts alone.
Par conséquent, pour ce temps de séjour très court, on observe de bons résultats en termes de conversion et de nitrilation avec une très faible différence entre ces deux valeurs, indiquant une faible teneur en sous-produits. Therefore, for this very short residence time, good results are observed in terms of conversion and nitrilation with a very small difference between these two values, indicating a low content of by-products.
Enfin, la figure 2 apporte la preuve de l'effet attendu lié aux valeurs du ratio volumique selon l'invention.  Finally, FIG. 2 provides the proof of the expected effect related to the values of the volume ratio according to the invention.
EXEMPLE 2 : Test sur l'ester méthylique de l'acide undécènoïque. EXAMPLE 2 Test on the methyl ester of undecenoic acid
Des tests ont été menés sur l'ester méthylique de l'acide undécènoïque et avec le catalyseur Fe203 sur un support A1203. Le mode opératoire est le même que celui-exposé dans l'exemple 1 ci- dessus. Tests were carried out on the methyl ester of undecenoic acid and with the Fe 2 O 3 catalyst on an Al 2 O 3 support . The procedure is the same as that set forth in Example 1 above.
Résultats : Results:
Cette expérience a été menée avec 3 catalyseurs différents : de l'alumine seule : A1203, de l'oxyde de fer seul : Fe203 et un mélange A1203/ Fe203 dans un ratio volumique Fe203/(A1203 + Fe203) de 0,5. This experiment was conducted with 3 different catalysts: alumina alone: Al 2 O 3 , iron oxide alone: Fe 2 O 3 and a mixture Al 2 O 3 / Fe 2 O 3 in a volume ratio Fe 2 0 3 / (Al 2 O 3 + Fe 2 O 3 ) of 0.5.
Le temps de séjour moyen est de 4,5 secondes. Les résultats en termes de conversion, de nitrilation, chacun exprimé en pourcentage molaire figurent dans les tableaux ci-dessous. The average residence time is 4.5 seconds. The results in terms of conversion, of nitrilation, each expressed in molar percentage are shown in the tables below.
2. 1 A 200°C 2. At 200 ° C.
Les résultats figurent dans le tableau 6 ci-dessous . The results are shown in Table 6 below.
Tableau 6  Table 6
Il est constaté que, même à 200°C, qui est une température relativement basse, le mélange de catalyseurs selon l' invention conduit à une augmentation pour la nitrilation surprenante et inattendue. It is found that even at 200 ° C, which is a relatively low temperature, the catalyst mixture according to the invention leads to a surprising and unexpected increase in nitrilation.
2.2 A 250°C 2.2 at 250 ° C
Les résultats figurent dans le tableau 7 ci-dessous. The results are shown in Table 7 below.
Tableau 7  Table 7
Ces résultats montrent une nette amélioration de la teneur en nitrilation pour le catalyseur selon l' invention comparé aux catalyseurs seuls. These results show a clear improvement in the nitrilation content for the catalyst according to the invention compared to catalysts alone.
Ces essais mettent en évidence l'effet inattendu et surprenant apporté par le catalyseur spécifique de l'invention qui comprend un mélange d'oxydes métalliques tel qu'il a été défini précédemment, dans le ratio de mélanges également précédemment défini. Les taux de conversion observés, ainsi que les taux de nitriles observés sont supérieurs à ceux obtenus avec les catalyseurs ne comprenant qu'un seul oxyde métallique . Ceci est d'autant plus surprenant que le temps de contact très court, évalué à quelques secondes : 4,5 sec. These tests highlight the unexpected and surprising effect provided by the specific catalyst of the invention which comprises a mixture of metal oxides as defined above, in the ratio of mixtures also previously defined. The conversion rates observed, as well as the nitrile levels observed, are higher than those obtained with catalysts comprising only one metal oxide. This is all the more surprising as the very short contact time, estimated at a few seconds: 4.5 sec.

Claims

REVENDICATIONS
1 . Procédé de nitrilation d' acide gras ou d' ester d' acide gras, éventuellement insaturé par action de l ' ammoniac dans un réacteur fonctionnant en continu en phase gaz ou en phase mixte gaz-liquide dans une gamme de température allant de 1 80 à 400°C , en présence d'un catalyseur solide comportant 1. Process for the nitrilation of fatty acid or fatty acid ester, optionally unsaturated by the action of ammonia in a reactor operating continuously in the gas phase or in the mixed gas - liquid phase in a temperature range of from 1 80 to 400 ° C, in the presence of a solid catalyst comprising
-au moins un oxyde métallique, dont le métal appartient à la co lonne 8 du tableau de la classification périodique en mélange avec at least one metal oxide, the metal of which belongs to column 8 of the periodic table in admixture with
-au moins un oxyde métallique choisi parmi les oxydes d' aluminium, les oxydes de zirconium, les oxydes de niobium, les oxydes de tantale et les oxydes d' étain, at least one metal oxide chosen from aluminum oxides, zirconium oxides, niobium oxides, tantalum oxides and tin oxides,
le ou les oxydes métalliques, dont le métal appartient à la co lonne 8 étant présent dans un rapport volumique de 0, 1 à 0,6 par rapport au vo lume du mélange de la totalité des oxydes.  the metal oxide or oxides, the metal of which belongs to column 8, being present in a volume ratio of 0.1 to 0.6 relative to the volume of the mixture of all the oxides.
2. Procédé selon la revendication précédente, caractérisé en ce que le catalyseur comporte au moins en tant qu'oxyde métallique, dont le métal appartient à la co lonne 8 du tableau de la classification périodique, de l 'oxyde ferrique.  2. Method according to the preceding claim, characterized in that the catalyst comprises, at least as metal oxide, whose metal belongs to the column 8 of the table of the periodic table, ferric oxide.
3. Procédé selon la revendication 1 ou 2, caractérisé en ce que le catalyseur comprend de l' oxyde ferrique (Fe2C"3 ) et du pentoxyde de niobium (Nb205) . 3. Method according to claim 1 or 2, characterized in that the catalyst comprises ferric oxide (Fe 2 C 3) and niobium pentoxide (Nb 2 0 5 ).
4. Procédé selon la revendication 1 ou 2, caractérisé en ce que le catalyseur comprend de l' oxyde ferrique (Fe203 ) et de l'oxyde d' aluminium (AI2O3) . 4. Method according to claim 1 or 2, characterized in that the catalyst comprises ferric oxide (Fe 2 O 3) and aluminum oxide (Al 2 O 3).
5. Procédé selon la revendication 1 ou 2, caractérisé en ce que le catalyseur comprend de l' oxyde ferrique (Fe203 ) et de l'oxyde de zirconium (Zr02) . 5. Method according to claim 1 or 2, characterized in that the catalyst comprises ferric oxide (Fe 2 O 3) and zirconium oxide (Zr0 2 ).
6. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que les réactifs du procédé sont des acides ou esters ω-insaturé de formule suivante :  6. Process according to any one of the preceding claims, characterized in that the reagents of the process are acides-unsaturated acids or esters of the following formula:
CH2=CH-(CH2)„-COOR CH 2 = CH- (CH 2 ) "- COOR
dans laquelle  in which
n représente l ' entier 7 ou 8 et R représente soit un atome d 'hydrogène, soit un radical alkyle comportant 1 à 4 atomes de carbone. n represents the integer 7 or 8 and R represents either a hydrogen atom or an alkyl radical having 1 to 4 carbon atoms.
7. Procédé selon l'une quelconque des revendications précédentes, caractérisé en ce que la température de réaction va de 200°C à 300°C, et de préférence de 200 à 250°C .  7. Method according to any one of the preceding claims, characterized in that the reaction temperature is from 200 ° C to 300 ° C, and preferably from 200 to 250 ° C.
8. Catalyseur so lide comportant  8. Solid catalyst with
-au moins un oxyde métallique, dont le métal appartient à la co lonne 8 du tableau de la classification périodique en mélange avec at least one metal oxide, the metal of which belongs to column 8 of the periodic table in admixture with
-au moins un oxyde métallique choisi parmi les oxydes d' aluminium, les oxydes de zirconium, les oxydes de niobium, les oxydes de tantale et les oxydes d' étain, at least one metal oxide chosen from aluminum oxides, zirconium oxides, niobium oxides, tantalum oxides and tin oxides,
-le ou les oxydes métalliques, dont le métal appartient à la co lonne 8 étant présent dans un rapport volumique de 0, 1 à 0,6 par rapport au volume du mélange de la totalité des oxydes.  or the metal oxides, the metal of which belongs to column 8 being present in a volume ratio of 0.1 to 0.6 relative to the volume of the mixture of all the oxides.
9. Catalyseur selon la revendication 8 , caractérisé en ce que l'oxyde métallique, dont le métal appartient à la co lonne 8 du tableau de la classification périodique est l ' oxyde ferrique.  9. Catalyst according to claim 8, characterized in that the metal oxide, the metal of which belongs to column 8 of the periodic table is ferric oxide.
10. Catalyseur selon la revendication précédente, caractérisé en ce qu' il comprend de l 'oxyde ferrique (Fe203) et du pentoxyde de niobium (Nb205) . 10. Catalyst according to the preceding claim, characterized in that it comprises ferric oxide (Fe 2 O 3 ) and niobium pentoxide (Nb 2 0 5 ).
1 1 . Catalyseur selon la revendication 9, caractérisé en ce qu' il comprend de l 'oxyde ferrique (Fe203) et de l ' oxyde d' aluminium (A1203) . 1 1. Catalyst according to claim 9, characterized in that it comprises ferric oxide (Fe 2 O 3 ) and aluminum oxide (Al 2 O 3 ).
12. Catalyseur selon la revendication 9, caractérisé en ce qu' il comprend de l 'oxyde ferrique (Fe203) et de l ' oxyde de zirconium12. Catalyst according to claim 9, characterized in that it comprises ferric oxide (Fe 2 O 3 ) and zirconium oxide.
(Zr02) . (Zr0 2 ).
13. Catalyseur selon l'une quelconque des revendications 8 à 13. Catalyst according to any one of claims 8 to
12, caractérisé en ce que la surface spécifique de ce catalyseur va de 10 à 500m2/g, de préférence de 40 à 300 m2/g. 12, characterized in that the specific surface area of this catalyst is from 10 to 500 m 2 / g, preferably from 40 to 300 m 2 / g.
14. Catalyseur selon l 'une quelconque des revendications 8 à 14. Catalyst according to any one of claims 8 to
13 , caractérisé en ce que le catalyseur est caractérisé par une distribution de taille des pores, telle que moins de 20 % du volume poreux soit dans des pores de diamètre inférieur à 2 nm, et de préférence inférieur à 3.5 nm, et de manière encore plus préférée inférieur à 7 nm. 13, characterized in that the catalyst is characterized by a pore size distribution, such that less than 20% of the pore volume is in pores less than 2 nm in diameter, and preferably less than 3.5 nm, and even more preferably less than 7 nm.
15. Procédé de préparation du catalyseur tel que défini à l 'une quelconque des revendications 8 à 14 comprenant une étape de mélange mécanique des oxydes métalliques .  15. Process for preparing the catalyst as defined in any one of claims 8 to 14, comprising a step of mechanical mixing of the metal oxides.
16. Utilisation du catalyseur tel que défini à l 'une quelconque des revendications 8 à 14 pour un procédé de nitrilation d' esters d' acides gras ou d' acides gras .  16. Use of the catalyst as defined in any one of claims 8 to 14 for a process for the nitrilation of esters of fatty acids or fatty acids.
EP14705194.0A 2013-02-20 2014-02-19 Gas-phase and liquid-gas-phase nitrilation process Ceased EP2958673A1 (en)

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US10287238B2 (en) 2019-05-14
FR3002227B1 (en) 2021-10-01
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JP2016513119A (en) 2016-05-12
US20160016153A1 (en) 2016-01-21

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