Classifications

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  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D309/00—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings
  • C07D309/02—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members
  • C07D309/08—Heterocyclic compounds containing six-membered rings having one oxygen atom as the only ring hetero atom, not condensed with other rings having no double bonds between ring members or between ring members and non-ring members with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D309/10—Oxygen atoms
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D307/00—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom
  • C07D307/02—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings
  • C07D307/26—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member
  • C07D307/30—Heterocyclic compounds containing five-membered rings having one oxygen atom as the only ring hetero atom not condensed with other rings having one double bond between ring members or between a ring member and a non-ring member with hetero atoms or with carbon atoms having three bonds to hetero atoms with at the most one bond to halogen, e.g. ester or nitrile radicals, directly attached to ring carbon atoms
  • C07D307/32—Oxygen atoms
  • C07D307/33—Oxygen atoms in position 2, the oxygen atom being in its keto or unsubstituted enol form
• • 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
  • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
  • B01J21/04—Alumina
• • 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
  • B01J21/063—Titanium; 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
  • 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
  • B01J21/08—Silica
• • 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
  • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
  • B01J23/40—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals of the platinum group metals
  • B01J23/46—Ruthenium, rhodium, osmium or iridium
• • 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
  • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
  • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/56—Platinum group metals
  • B01J23/62—Platinum group metals with gallium, indium, thallium, 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
  • B01J23/38—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals
  • B01J23/54—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of noble metals combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/56—Platinum group metals
  • B01J23/62—Platinum group metals with gallium, indium, thallium, germanium, tin or lead
  • B01J23/622—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead
  • B01J23/626—Platinum group metals with gallium, indium, thallium, germanium, tin or lead with germanium, tin or lead with tin
• • 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
  • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
• • 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
  • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
  • B01J35/51—Spheres
• • 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
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/0201—Impregnation
• • 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
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/0201—Impregnation
  • B01J37/0213—Preparation of the impregnating solution
• • 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
  • B01J37/16—Reducing
  • B01J37/18—Reducing with gases containing free hydrogen
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07D—HETEROCYCLIC COMPOUNDS
  • C07D313/00—Heterocyclic compounds containing rings of more than six members having one oxygen atom as the only ring hetero atom
  • C07D313/02—Seven-membered rings
  • C07D313/04—Seven-membered rings not condensed with other rings

Definitions

• the present invention relates to a process for preparing a lactone.
• the invention relates to the preparation of butyrolactone, valerolactone and caprolactone.
• lactone in the present text is meant a compound which is characterized by the presence of an ester function in a ring.
• Lactones are compounds that find many applications in the industry, especially as intermediates for the preparation of molecules in the pharmaceutical or agrochemical fields.
• Lactones also find application as a solvent or can be used in the polymer field as monomers.
• An access route to lactones consists in carrying out an intramolecular esterification of a bifunctional compound carrying a carboxylic function and an alcohol function.
• US Pat. No. 6,838,577 describes the preparation of lactones comprising 4 or 5 atoms by heating the corresponding hydroxy acids resulting in the loss of a water molecule and the spontaneous cyclization (comparative example) or by heating in the presence of a catalyst.
• a catalyst such as silica, alumina and mixtures thereof.
• lactones in particular ⁇ -butyrolactone
• GB 583 344 can be prepared according to GB 583 344 from the corresponding diol by dehydrogenation in the gas phase, in the presence of a copper or silver catalyst.
• lactones can be prepared according to the Baeyer-Villiger reaction, by reaction of a cyclic ketone with a peroxide or an organic peracid obtained from a carboxylic acid, generally acetic acid and hydrogen peroxide.
• a catalyst which may be an acidic cation exchange resin (Amberlyst 15) or zeolites (H-ZSM-5, H-mordenite, USY).
• the object of the present invention is to provide a novel lactone preparation process involving a totally different substrate.
• a process for the preparation of a lactone characterized in that it comprises the reduction of a dicarboxylic acid using hydrogen. in the gaseous phase and in the presence of an effective amount of a catalyst comprising a ruthenium-tin active phase composed of at least one Ru 2 Sn 3 alloy and an Ru 3 Sn 7 alloy.
• Another object of the present invention is the cyclizing hydrogenation catalyst involved in the process of the invention.
• a dicarboxylic acid which more particularly corresponds to the following formula (I):
• R represents a divalent group, substituted or unsubstituted, comprising a linear sequence of atoms in a number sufficient to form the desired lactone.
• sequence of atoms is meant the atoms that intervene in the cycle, the substituents being excluded.
• the group R comprises a linear sequence of 2 to 8 atoms and preferably of 2 to 6 atoms and even more preferably of 2 to 4. It is most often a sequence of carbon atoms but the invention does not exclude that the hydrocarbon chain is interrupted by a heteroatom, especially nitrogen, oxygen or sulfur.
• the divalent R group may be substituted, that is to say that the hydrogen atoms of the hydrocarbon chain may be replaced by a group or an organic function. Any substituents may be present to the extent that they do not interfere with the cyclization reaction.
• the hydrocarbon chain may carry a substituent such as, for example, a hydroxy group or a halogen atom, preferably fluorine, chlorine or bromine, or carry side chains or branches which may preferably consist of alkyl groups which generally have 1 to 4 carbon atoms. The branches are most often located on one or both carbon atoms at the ⁇ or ⁇ position of the carboxylic groups.
• the group R has a total carbon condensation which can vary widely from 2 carbon atoms to a number which can be up to 15 carbon atoms when there is presence of substituents and said group comprises a linear sequence of 2 to 8 atoms which intervenes then in the obtained cycle.
• R preferably represents a linear or branched saturated or unsaturated divalent aliphatic group.
• R represents a linear or branched saturated aliphatic group preferably having from 2 to 15 carbon atoms or a linear or branched unsaturated group comprising one to more unsaturations on the chain, generally 1 or 2 unsaturations which may be preferably, single or conjugated double bonds.
• dicarboxylic acids of general formula (I) in which the aliphatic group R is a linear or branched alkylene group having from 2 to 12 carbon atoms, which comprises a chain, are particularly suitable for carrying out the process of the invention. linear from 2 to 8 carbon atoms between the two COOH groups.
• the preferred R group comprises a linear sequence of 2 to 4 carbon atoms between the two COOH groups.
• ring is meant a carbocyclic or heterocyclic ring, saturated, unsaturated or aromatic.
• rings it is possible to envisage cycloaliphatic, aromatic or heterocyclic rings, in particular cycloalkyl rings comprising 6 ring carbon atoms or benzenes, which rings may themselves be optionally substituted with one or more substituents, insofar as they do not do not interfere with the cyclization reaction.
• R groups examples include, but are not limited to, the following groups:
• carboxylic acids of formula (I) which are suitable for the present invention, the following dicarboxylic acids are more particularly used:
• pimelic acid (heptanedioic acid)
• succinic acid succinic acid
• glutaric acid glutaric acid
• malic acid succinic acid
• the cyclization reaction of the dicarboxylic acid is carried out in the presence of the catalyst of the invention which is a cyclizing hydrogenation catalyst.
• the active phase of the catalyst of the invention comprises ruthenium-tin alloy phases.
• the ruthenium and tin are advantageously in the form of an Ru 2 Sn 3 alloy mixed with the P ⁇ Sn / alloy.
• the active phase comprising ruthenium and tin has an atomic ratio Sn / Ru at least equal to 3/2, preferably to 9/5.
• the Sn / Ru atomic ratio is less than 7/3, advantageously 6.5 / 3 and even more preferably 2/1.
• the active phase consists mainly of the alloy phase Ru 2 Sn 3 .
• the active phase comprises at least 75% by weight of the Ru 2 Sn 3 alloy, the composition of the other active phase fraction depends on the Sn / Ru atomic ratio.
• the atomic ratio Sn / Ru equal to 1, 5 corresponds theoretically to an active phase of pure Ru 2 Sn 3 .
• the alloy phase Ru 2 Sn 3 is accompanied by the alloy phase Ru 3 Sn 7 .
• the Sn / Ru atomic ratio decreases and becomes less than 1.5
• the allied Ru 2 Sn 3 and Ru 3 Sn 7 phases are accompanied by a ruthenium metal phase.
• the ruthenium metal phase represents less than 10% by weight of the ruthenium-tin active phase.
• the invention also includes the case where the active phase comprises at the same time the alloyed phases Ru 2 Sn 3 and Ru 3 Snz and ruthenium metal.
• the invention does not exclude the case of the presence of other compounds (such as for example ruthenium oxide) in minor amounts representing less than 10% by weight, preferably less than 5% of the active phase.
• the support must be chosen so as to maximize the resistance to industrial conditions, and in particular the resistance to mechanical abrasion, in particular the resistance to attrition.
• the support must be chosen so as to avoid significant pressure losses, while allowing good contact between the gas and the catalyst.
• the carrier must be inert to the reaction mixture.
• the support must be chosen from compounds or compositions that induce little or no parasitic reactions
• the support may be in any form, for example, powder, beads, granules, extrudates ...
• the support may be chosen in particular from metal oxides, such as oxides of aluminum, silicon, titanium and / or zirconium or their mixtures.
• Mixed oxides are also suitable and more particularly those containing at least 1/4, advantageously 1/3, preferably 2/5 by weight of aluminum, expressed as Al 2 O 3.
• the support advantageously has a silicon content which is expressed as SiO 2, which is at most equal to 2/3 of the total weight, advantageously at most equal to 1/4.
• the specific surface of the BET support is advantageously chosen between 5 and 100 m 2 / g and preferably between 10 and 50 m 2 / g.
• the ruthenium content of the catalyst is advantageously chosen between 1 and 8% by weight, and even more preferably between 2 and 3% by weight.
• said ruthenium-tin active phase is composed of at least one Ru 2 Sn 3 alloy and an Ru 3 Sn 7 alloy,
• the alloy phase Ru 2 Sn 3 represents at least 75% by weight of the ruthenium-tin active phase
• At least 90% by weight of the ruthenium is in an alloy form Ru 2 Sn 3 and Ru 3 Sn 7.
• the alloy phase Ru 2 Sn 3 represents at least
• ruthenium is present in a form at least 90%, preferably at least 95%, and more preferably at least 98%.
• One of the modes of the preparations of said ruthenium-tin catalyst is to carry out the reduction of a ruthenium complex having a 4-electrovalence and a coordination number of 6, the ligands being either a halogen atom or a dicarboxylic acid anion. a tin halide.
• the reduction of a complex more particularly corresponds to the following formula (A):
• X represents a halogen atom, preferably a chlorine or bromine atom and n is a number equal to 1 or 2, and preferably equal to 2.
• the complex (s) is prepared by reacting a ruthenium halide and a tin halide in the presence of an acid.
• ruthenium halide III preferably a ruthenium III chloride. It is also possible to start from a ruthenium IV salt but there is no additional advantage especially since it is more expensive.
• ruthenium halide III which can be indifferently in anhydrous or hydrated form.
• said compound does not contain too many impurities.
• a compound which is free of heavy metals and has a chemical purity of 99% ruthenium relative to other metals is used.
• tin salt a tin halide is used in which the tin has a lower degree of oxidation than ruthenium.
• a tin halide II preferably a tin II chloride
• the salt is also possible to use the salt in anhydrous or hydrated form.
• the commercial tin salt of formula SnCl 2 , 2H 2 O is also used.
• the halides of said metals are used in the form of an aqueous solution.
• concentration of these solutions is such that one obtains a homogeneous solution that can be impregnated on a support.
• the ratio between the number of moles of tin halide and the number of moles of ruthenium halide varies between 1 and 5, and preferably between 2 and 4.
• the active phase of the catalyst obtained comprises the alloy phase Ru 2 Sn 3 which is accompanied by an allied phase Ru 2 Sn 7 .
• the catalyst advantageously used in the process of the invention results from the use of tin halides and ruthenium so that their molar ratio is between 2 and 4.
• the preparation of the complex by reaction of the ruthenium and tin halides is carried out in the presence of an acid whose function is to solubilize the tin halide and to maintain the formed complex soluble.
• hydrochloric acid is generally the preferred acid.
• the amount of acid used is preferably at least 1 mole of acid per mole of ruthenium halide, and more preferably between 1 to 5 moles of acid per mole of ruthenium halide.
• the upper limit is not critical and can be exceeded without inconvenience.
• the preferred amount of acid is about 3 moles of acid per mole of ruthenium halide.
• the preparation of the complex is done by mixing, in any order, the ruthenium halide (from preferably, ruthenium chloride III) of tin halide (preferably tin chloride II) and strong acid (preferably hydrochloric acid).
• the ruthenium halide from preferably, ruthenium chloride III
• tin halide preferably tin chloride II
• strong acid preferably hydrochloric acid
• the reaction mixture is heated at a temperature of 60 ° C to 100 ° C, preferably at 70 ° C to 95 ° C.
• duration of this operation can vary widely and it is specified for illustrative purposes, a duration ranging from 1 to 3 hours is quite suitable.
• the complex is formed quite quickly but it remains in solution.
• the temperature is brought back to ambient temperature, that is to say at a temperature most often between 15 ° C. and 25 ° C.
• the complex solution thus obtained serves to prepare the catalyst of the invention in particular for depositing the active phase on the support.
• the solution of the complex obtained above is used in the case of the preparation of a supported catalyst, to deposit the active phase on the support according to an impregnation technique.
• the supported metals are deposited by impregnating said support with the solution of the complex obtained according to the process described above.
• the aqueous impregnating solution comprises the ruthenium-tin complex in a proportion of 1% to 20% by weight of ruthenium.
• the impregnation can be carried out by spraying on the support set in motion, for example, by the rotation of a bezel, the solution comprising the ruthenium and tin complex.
• the impregnation is carried out "dry", that is to say the total volume of the complex solution used is approximately equal to the pore volume presented by the support.
• the pore volume it can be done according to any known technique, including the mercury porosimeter method (ASTM D 4284-83) or measure on a sample, the amount of water it absorbs.
• the impregnated support is then subjected to a reduction operation.
• a preferred variant of the invention consists in first carrying out a drying step.
• the drying is carried out most often in air at a temperature which can range from ambient temperature, for example 20 ° C. to 100 ° C.
• the drying time is continued until a constant weight is obtained.
• the reduction of the complex is carried out by bringing the impregnated support into contact with the reducing agent.
• the hydrogen can be injected at atmospheric pressure or under a slight pressure, for example from 0.5 to 10 bar, preferably from 1 to 2 bar.
• Hydrogen can also be diluted in an inert gas such as nitrogen or helium.
• the reduction reaction is carried out at a temperature of at least 400 ° C., preferably between 400 ° C. and 600 ° C., and even more preferably between 400 ° C. and 500 ° C.
• the reduction can also be carried out during the implementation of the catalyst in the event that it is implemented in a reduction reaction of a substrate in the presence of hydrogen.
• the catalyst obtained can be used in the process for preparing a lactone according to the invention.
• the solution of the complex obtained above can be used to deposit the active phase on support by the precipitation technique.
• another method of preparation consists, when the support is in the form of a powder, such as, for example, alumina, silica or a metal oxide, to add the support to the solution of the complex obtained, to conduct the reaction. hydrolyzing the previously obtained complex and then separating the solid obtained, preferably by filtration and kneading and extruding. A shaped catalyst is thus obtained.
• a powder such as, for example, alumina, silica or a metal oxide
• the hydrolysis of the complex is obtained by adding water.
• the quantity of water used is not critical: it generally represents 1 to 100 times the weight of the complex.
• the complex precipitates and is separated and shaped as described above.
• the catalyst thus obtained can be subjected as previously described for the impregnated support to a drying and reduction operation and, if necessary, can be activated during its use.
• the process of the invention is carried out in the gas phase.
• the reaction is carried out at a temperature of between 270 ° C. and 450 ° C., and even more preferentially between 300 ° C. and 400 ° C. It is understood that the temperature is adapted by the skilled person depending on the starting acid, and the desired reaction rate.
• the catalyst may be preliminarily subjected to temperatures of about 500 ° C., and preferably of 450 ° C.
• the activation is advantageously carried out under a stream of hydrogen.
• the hydrogen can be injected at atmospheric pressure or under a slight pressure compatible with the vapor phase (a few bars, for example from 0.5 to 10 bar). Hydrogen can also be diluted in an inert gas such as nitrogen or helium.
• the hydrogen is injected at a flow rate of between 0.1 and 10 liters per hour, and the acid at a liquid flow rate of at most 10 ml / h, and preferably between 0 , 5 and 5 ml / h.
• a practical way of carrying out the present invention is to introduce into a reactor a desired amount of catalyst.
• the temperature of the reactor is then raised under a stream of hydrogen to a predetermined value, preferably 450 ° C. to 500 ° C., to activate the catalyst, then to bring it to a reaction temperature of preferably 300 ° C. to 400 ° C. vs.
• the acid is then injected at the desired rate and the lactone formed is recovered.
• the contact time which is defined as the ratio between the apparent volume of catalyst and the flow rate of the gas stream (which includes the carrier gas) can vary widely, and is most often between 0.2 and 50 seconds.
• the contact time is preferably chosen between 0.4 and 10 seconds.
• the reaction is easily carried out continuously by passing the gas stream through a tubular reactor containing the catalyst. It begins by preparing the catalyst bed which is constituted by the catalytic active phase deposited on a support (for example, sintered glass or grid) which allows the flow of gas without elution of the catalyst. Then, the dicarboxylic acid is contacted with the catalyst according to several possible variants.
• a first embodiment is to inject the acid after being vaporized by heating.
• Another embodiment of the invention is to inject the dicarboxylic acid in solution in an organic solvent.
• polar, protic or aprotic organic solvents may be mentioned as solvents.
• the amount of solvent is such that generally the dicarboxylic acid (I) represents from 30 to 60% of the mass of the reaction mixture (acid + solvent).
• the lactone is recovered from this gas stream, according to commonly used techniques.
• Said stream can be distilled directly at the reaction outlet and is generally obtained at the top of distillation, the hydrogen, the optional solvent and then the lactone and distillate, the dicarboxylic acid.
• the ester which forms with the dicarboxylic acid is also obtained.
• Said ester generally distills after the alcoholic solvent and before the lactone.
• Another variant consists in condensing said stream for example by cooling with a heat-transfer liquid (for example water at 20 ° C.) and then the lactone is recovered from the condensed stream by distillation or by liquid-liquid extraction.
• a heat-transfer liquid for example water at 20 ° C.
• the degree of conversion (TT) corresponds to the ratio between the number of moles of substrate [dicarboxylic acid] transformed and the number of moles of substrate [dicarboxylic acid] involved.
• the yield (RR) corresponds to the ratio between the number of moles of product formed (lactone) and the number of moles of substrate [dicarboxylic acid] involved.
• the medium is then heated with stirring at 90 ° C. and maintained under these conditions for one hour.
• the complex solution is then brought back to room temperature.
• the beads are then dried in a ventilated oven to constant weight. Ten grams of impregnated beads are then introduced into a tubular glass reactor 22 mm in diameter.
• This stream of catalyst is then passed through a stream of 3 l / h of hydrogen with gradual heating to 450 ° C.
• the catalyst is then cooled to room temperature and stored as.
• the beads are then dried in a ventilated oven to constant weight.
• This stream of catalyst is then passed through a stream of 3 l / h of hydrogen with gradual heating to 450 ° C.
• the catalyst is then cooled to room temperature and stored as.
• the procedure used to prepare the catalyst 1 is repeated but using a commercial pelletized anatase titanium oxide.
• the catalytic bed is heated under a stream of 5 l / h of hydrogen at 375 ° C. After stabilization of the catalytic bed under these conditions for 30 minutes, an aqueous solution of 40% w / w glutaric acid at a flow rate of 6 is injected onto the catalytic bed and with the aid of a syringe pump. ml / h.
• reaction gas stream is then condensed in a receiver immersed in a water-ice bath.
• the catalytic bed is heated under a stream of 5 l / h of hydrogen at 375 ° C. After stabilization of the catalytic bed under these conditions for 30 minutes, a methanolic solution of glutaric acid at 50% w / w is injected onto the catalyst bed and with the aid of a syringe pump at a flow rate of 10%. ml / h. The reaction gas stream is then condensed in a receiver immersed in a water-ice bath.
• the catalytic bed is heated under a flow of 10 l / h of hydrogen at 375 ° C.
• a methanolic solution of glutaric acid at 50% w / w at a flow rate of 10 ml / h is injected onto the catalytic bed and with the aid of a syringe pump.
• reaction gas stream is then condensed in a receiver immersed in a water-ice bath.
• the catalytic bed is heated under a stream of 5 l / h of hydrogen at 375 ° C. After stabilization of the catalytic bed under these conditions for 30 minutes, an aqueous solution of 40% w / w glutaric acid is started on the catalytic bed and with the aid of a syringe pump at a flow rate of 10%. ml / h.
• reaction gas stream is then condensed in a receiver immersed in a water-ice bath. After 5 hours of injection under these conditions, the GC is analyzed by the condensates.
• the catalytic bed is heated under a stream of 5 l / h of hydrogen at 375 ° C. After stabilization of the catalytic bed under these conditions for 30 minutes, a methanolic solution of glutaric acid at 50% w / w is injected onto the catalyst bed and with the aid of a syringe pump at a flow rate of 10%. ml / h.
• reaction gas stream is then condensed in a receiver immersed in a water-ice bath.
• the catalytic bed is heated under a flow of 10 l / h of hydrogen at 375 ° C.
• a methanolic solution of glutaric acid at 50% w / w at a flow rate of 10 ml / h is injected onto the catalytic bed and with the aid of a syringe pump.
• reaction gas stream is then condensed in a receiver immersed in a water-ice bath.
• the catalytic bed is heated under a flow of 10 l / h of hydrogen at 375 ° C.
• reaction gas stream is then condensed in a receiver immersed in a water-ice bath.
• the catalytic bed is heated under a stream of 5 l / h of hydrogen at 375 ° C. After stabilization of the catalytic bed under these conditions for 30 minutes, a solution of 30% w / w glutaric acid in dimethoxyethane is injected onto the catalytic bed and using a syringe pump at a rate of 10 ml / h.
• reaction gas stream is then condensed in a receiver immersed in a water-ice bath.
• the catalytic bed is heated under a stream of 5 l / h of hydrogen at 375 ° C. After stabilization of the catalyst bed under these conditions for 30 minutes, an aqueous solution of adipic acid at 2% w / w at a flow rate of 10% w / w was started on the catalyst bed and with the aid of a syringe pump. ml / h.
• reaction gas stream is then condensed in a receiver immersed in a water-ice bath.
• Example 4 is repeated using the catalyst prepared on titanium oxide.
• Example 4 is repeated using the catalyst 6 prepared on titanium oxide.
• the catalytic bed is heated under a stream of hydrogen of 5 l / h at 300 ° C. After stabilization of the catalyst bed under these conditions for 30 minutes, an aqueous solution of malic acid at 30% w / w is started on the catalytic bed at a flow rate of 8 ml / h.
• the gaseous reaction stream is then condensed in a receiver immersed in an ice-water bath.
• the catalytic bed is heated to 375 ° C. under a stream of hydrogen of 5 l / h and after stabilization of the catalyst bed for 30 min, a 40% w / w aqueous solution of glutaric acid is first injected. flow rate of 1 ml / h.
• the gaseous reaction stream is condensed in a receiver immersed in an ice-water bath.

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