WO2013004509A1 - Solid/liquid heterogeneous catalysis in a millifluidic or microfluidic medium - Google Patents

Solid/liquid heterogeneous catalysis in a millifluidic or microfluidic medium Download PDF

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Publication number
WO2013004509A1
WO2013004509A1 PCT/EP2012/061926 EP2012061926W WO2013004509A1 WO 2013004509 A1 WO2013004509 A1 WO 2013004509A1 EP 2012061926 W EP2012061926 W EP 2012061926W WO 2013004509 A1 WO2013004509 A1 WO 2013004509A1
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Prior art keywords
liquid
drops
catalyst
stream
flow member
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PCT/EP2012/061926
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French (fr)
Inventor
Flavie Sarrazin
Kévin OLIVON
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Rhodia Operations
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Publication of WO2013004509A1 publication Critical patent/WO2013004509A1/en

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0093—Microreactors, e.g. miniaturised or microfabricated reactors
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00788—Three-dimensional assemblies, i.e. the reactor comprising a form other than a stack of plates
    • B01J2219/00792—One or more tube-shaped elements
    • B01J2219/00797—Concentric tubes
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00819—Materials of construction
    • B01J2219/00833—Plastic
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00851—Additional features
    • B01J2219/00858—Aspects relating to the size of the reactor
    • B01J2219/00862—Dimensions of the reaction cavity itself
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00889—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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00891—Feeding or evacuation
    • B01J2219/00894—More than two inlets
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/00891—Feeding or evacuation
    • B01J2219/00903—Segmented flow
    • 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
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00781—Aspects relating to microreactors
    • B01J2219/0095—Control aspects
    • B01J2219/00952—Sensing operations
    • B01J2219/00968—Type of sensors
    • B01J2219/0097—Optical sensors

Definitions

  • the present invention relates to a process employing a reaction employing a solid catalyst within a heterogeneous liquid reaction medium (hereinafter referred to as "solid / liquid catalysis”) and carried out under specific conditions, namely in controlled size drops, conveyed in a carrier liquid (continuous liquid carrier phase), in a tubular reactor of millimeter or micrometer section greater than that of the drops.
  • solid / liquid catalysis a heterogeneous liquid reaction medium
  • This particular method which implements solid / liquid catalysis within the drops, which behaves as microreactors of reduced size (typically of the order of a few nanoliters to a few microliters) can, among other things, be used to acquire data on the reaction of solid / liquid catalysis that takes place within the drops, by determining at least one physical and / or chemical parameter of the medium contained in the drops, these data proving to be an excellent reflection of those obtained on a more macroscopic scale in larger stirred reactors ("batch" reactors with a volume much greater than that of drops, with a volume of at least several hundred ml, or even several liters, or more ) implementing the same solid catalyst dispersed in the same liquid reaction medium.
  • the solid / liquid catalysis reactions are of great interest, particularly for the intermediates and specialty or fine chemicals industry, in particular for the advantages it offers in terms of catalyst recyclability and savings. in the purification steps of the final products.
  • To best select a solid catalyst well suited to a given chemical reaction it is desirable to acquire the most data on different catalysts (chemical activity of the catalyst, kinetics of the reaction, degradation of the catalyst, etc.).
  • this acquisition of the data passes by tests carried out on agitated 'batch' reactors, which require large quantities of material, which is problematic in particular when it is desired to test expensive catalysts or else when one only has access to a small sample.
  • the tests often need to be repeated several times, which results in a relatively long data acquisition time. It therefore appears that there is a need for a data acquisition system that would reduce the amount of catalyst to be used and the time required for acquisition.
  • microreactors appear attractive as a solid / liquid catalysis reaction modeling tool on a larger scale. Indeed, given their small size, they allow, among other things, to operate the reaction with a very small amount of catalyst. Nevertheless, the data collected on heterogeneous catalysis with this type of microreactor do not prove directly transferable to a macroscopic agitated system.
  • An object of the present invention is to provide a reactor having the advantages described above for the wall and fixed bed microreactors described above in terms of reducing the amount of catalyst needed for data acquisition, but which to obtain directly information reflecting the properties of the catalyst tested when it is implemented more quantitatively in a stirred reactor.
  • the present invention proposes the use of a specific microreactor, implementing the solid / liquid catalysis reaction within drops conveyed in a liquid carrier phase within a flow member, typically a capillary or a fluidic channel.
  • the subject of the present invention is a process which comprises a step (E) in which a chemical reaction is carried out employing at least one liquid or solubilized reagent, in a liquid reaction medium and in the presence of a catalyst. solid, characterized in that, in said step (E):
  • said liquid reaction medium is used in the form of drops conveyed within a continuous liquid carrier phase immiscible with said reaction medium, the flow of which is forced through a tubular flow member having a section whose largest dimension is less than 1 cm, preferably less than or equal to 5 mm, said drops having dimensions smaller than that of the internal diameter of the flow member;
  • the solid catalyst is implemented in the dispersed state within said drops, preferably without the presence of catalyst elsewhere than in said drops.
  • the section of the flow member whose largest dimension is less than 1 cm is the cross-section of the flow member, typically, the internal diameter of the flow member is inside 1 cm, preferably less than or equal to 5 mm.
  • the solid catalyst is implemented in the dispersed state within nanometric or millimetric drops playing, in a way, the role of miniaturized reactors.
  • the drops conveyed according to the invention in the flow member are smaller in size than the internal section of said flow member and, preferably, they are not in contact with the walls of the flow member. .
  • the drops are most often completely surrounded by the carrier liquid phase, which thereby inhibits any edge effects with the internal wall of the flow member.
  • the drops implemented according to the invention which are surrounded by a continuous liquid carrying phase, are to be distinguished from liquid 'plugs' which would be introduced into the flow member and which would be separated from each other by zones discontinuous liquid phase.
  • step (E) the reaction medium behaves substantially as it would do it in a stirred reactor more macroscopic.
  • the method of the invention can in particular be used to determine parameters of the chemical reaction in the presence of the catalyst, these parameters being transferable to the behavior of the catalyst in more macroscopic reactors, which thus makes it possible to determine the properties of the catalyst.
  • a catalyst by having to use a very limited amount.
  • the present invention relates to the aforementioned method, wherein step (E) further comprises measuring at least one physical and / or chemical characteristic of the solid / liquid medium contained in at least one of the drops.
  • This measurement can for example be carried out by means of on-line analysis devices (spectrometric probes for example), which, thanks to the space-time equivalence in the device for implementing the method of the invention (described more in detail below), allow to have in a single experiment different points of chemical kinetics.
  • the measurement can be carried out by means of off-line analyzes, in particular by taking a sample at the outlet of the flow member.
  • the process of the invention can be carried out with any type of dispersible solid catalyst, for example zeolites, in particular chosen from USYs (especially Y760 and / or Y720) and / or Beta or even supported metals, for example on charcoal (especially palladium supported on charcoal).
  • step (E) it is very easy to obtain the dispersion of this catalyst in the drops, as sought in step (E). For this purpose, it is most often sufficient to force the flow within the flow member with a flow rate sufficient to induce the desired dispersion.
  • An increase in the flow rate is accompanied by an increase in internal movements within the drops, related to forced convection by the walls of the flow member, which are sufficient to maintain the catalyst in suspension, substantially in the same way that it would be in a stirred reactor more macroscopic.
  • the process may optionally be conducted using, in addition to the flow, other additional means for suspending the solid catalyst, for example by subjecting the reaction medium comprising the catalyst with ultrasound, or else with a magnetic field (by using catalysts with magnetic character and / or by adding in the medium of the particles with magnetic character). Most often, such additional means for suspending the solid catalyst are not necessary according to the invention.
  • the liquid carrier phase used in the context of the present invention has a viscosity greater than that of the liquid reaction medium of the drops.
  • the ratio of the viscosity of the liquid carrier phase to that of the liquid reaction medium drops is not too high, otherwise there are risks, particularly with high flow rates, so that Droplet interfaces deform and catalyst particles are ejected from the drops.
  • the ratio of the viscosity of the liquid carrier phase relative to that of the liquid reaction medium of the drops is between 2 and 1000, preferably between 4 and 600, in particular between 5 and 500, this ratio being more preferably greater than 100, and more preferably still greater than or equal to 250 or even 300, although it is also possible to work outside these ratios.
  • step (E) despite its miniaturized nature, does not lead to an axial dispersion of the solid, as far as where it flows with the drops and is thus driven "in one block" in the current of the liquid carrier phase.
  • the method of the invention is not subject to the transfer phenomena that are observed with the prior art wall catalysis, nor to the presence of preferential paths as in the case of catalysts employed. in fixed bed.
  • the drops are formed continuously within the carrier liquid phase.
  • the drops are formed by sequentially or continuously injecting the liquid reaction medium containing the particles (or, more advantageously, by sequentially or continuously co-injecting several separate streams, the mixture of which forms the liquid reaction medium containing the particles). , within a continuous flow of liquid carrier phase conveyed within the flow member.
  • the injection or the co-injection of several streams
  • the drops are obtained by using suitable flow rates, according to a method well known per se, described for example in the application FR 2 907 030.
  • This embodiment allows in particular to control the size and speed of drops.
  • the injection into the continuous stream of liquid carrier phase is carried out by means of an injection system opening into the heart of the flow member, which makes it possible to obtain particles that are not in contact with the walls of the the flow member.
  • the reagents and catalyst are preferably introduced separately, so that they come into contact only at the time of formation of the drop, which allows to determine the initial time when the reaction begins. To do this, one can typically co-inject sequentially or continuously:
  • a first feed stream comprising at least one reagent used in the chemical reaction of step (E), in the liquid or solubilized state, said first stream comprising no catalyst;
  • the second feed stream containing the catalyst is most often constituted by the dispersed catalyst in a dispersing medium or it comprises the catalyst in the dispersed state and one or more reagent (s) distinct (s) of the reagent (s) present in the first introduction stream.
  • One or more streams may optionally be co-injected in addition to the two flows described above, for example a third stream comprising a reagent other than that of the first stream.
  • the drops of reaction medium are formed within the flow member by means of an injection system opening into said flow member and comprising two tubular pipes, namely:
  • a first tubular pipe (hereinafter referred to as an "outer tube") conveying a first stream comprising at least one reagent, liquid or solubilized, used in the reaction of step (E);
  • a second tubular duct located in said first tubular duct (typically, the inner tube and the outer tube are coaxial) and conveying a second stream comprising the catalyst in the dispersed state, and optionally one or more reagent (s) distinct (s) reagent (s) present (s) in the first feed stream.
  • This inner tube preferably has an internal diameter greater than or equal to 5 times (preferably greater than or equal to 10 times, and more preferably greater than or equal to 20 times) the size of the solid objects
  • the internal diameter of the inner tube is at least 100 microns, preferably at least 200 microns (for example of the order of 500 microns).
  • a conduct of the method of the invention according to the aforementioned continuous mode also authorizes a rapid change of the operating parameters during data acquisition relating to the chemical reaction and to the catalyst studied, which makes it possible to acquire different information without having to do this to stop the process.
  • each drop conveyed in the flow member behaves like an individual reactor where the operating conditions can vary with respect to a neighboring drop, which allows direct comparisons in strictly the same conditions of temperature and pressure .
  • This possibility of multiple measurements and direct comparison represents yet another very interesting advantage of the method of the invention, especially with respect to the processes implemented on a larger scale.
  • the process of the invention also has the advantage of being very flexible, both in terms of the nature of the catalyst, the reactants and the liquid phases, as well as with regard to the operating conditions.
  • the carrier liquid phase is inert with respect to the chemical reaction. That being the case, apart from this condition (and the fact that the carrier liquid phase must be immiscible with the liquid reaction medium of the drops), the catalyst, the reagents used in the chemical reaction and the different liquid phases present in the step (E) can vary to a very large extent.
  • the reactants and optional solvents of the organic phase can be both hydrophilic and hydrophobic.
  • the carrier liquid phase is a fluorinated oil, in particular of the type of the oil marketed under the name of IKV. fluorine by the company IKV tribology.
  • the internal wall of the flow member comprises, at least on the surface, a fluorinated organic material, for example of the Teflon type.
  • the carrier liquid phase may be a silicone oil.
  • step (E) can be implemented in a wide range of pressures and temperatures. Typically, step (E) can be carried out at pressures ranging from 1 to 30 bars, typically under pressure, at a pressure preferably of less than or equal to 20 bars, typically between 1.5 and 10 bars. Furthermore, step (E) may be carried out at temperatures up to 200 ° C, for example between 10 and 150 ° C.
  • the attached figure is a schematic representation in section of a device 1 for implementing the method of the invention, said millireactor.
  • This device comprises a flow member 10, representative of the flow members that can be used according to the invention. It is in the form of a cylindrical tube, capillary type, but other tubular members could be used.
  • the flow member used according to the invention has a section whose largest dimension is less than 1 cm, preferably less than 5 mm, for example between 0.5 and 4 mm. In particular when it is a cylindrical tube as shown in the Figure, its internal diameter is typically between 1 and 3 mm.
  • the flow member implemented according to the invention advantageously has a transparent character on all or part of its length, which allows in particular an observation of the flow that takes place and the behavior within the drops.
  • the flow member is entirely constituted by a transparent material.
  • transparent character is meant here, in the broad sense, that the flow member is formed by one or more materials whose physico-chemical nature allows the observation and / or the desired measurement and does not constitute a screen total to this observation and / or this measurement. It is not necessarily an optical transparency, nor a total transparency.
  • the flow member implemented according to the invention may typically be a plastic tube such as PTFE or PFA.
  • its internal surface preferably comprises, at least on the surface, a fluorinated organic polymer such as Teflon.
  • the length of the flow member implemented according to the invention can vary to a large extent.
  • the inventors have highlighted that the flow within this flow member remains generally stable even for very long lengths.
  • the flow member is a cylindrical tube of the capillary type as shown in the Figure, it may have a length of between 0.5 and 10 meters, in particular between 1 and 3 meters, knowing that the flow remains stable for larger dimensions.
  • the flow member 10 shown in the Figure is provided with a feed channel 1 1 provided with feed means (not shown) which allow the introduction into the flow member of a carrier liquid phase then its flow from the inlet 12 of said member to its outlet 13.
  • the flow member 10 is provided with an injection system 20 opening at an injection zone 25 located within the internal space of the flow member where a the flow of the carrier liquid phase.
  • this injection system comprises two tubes, namely: an outer tube 30, provided with a supply channel 31 provided with feed means (not shown) which allow the introduction into said outer tube 30 of a first flow comprising at least one reagent implemented in the chemical reaction of step (E) and not comprising a catalyst, then its flow from the inlet 32 of said outer tube to the injection zone 25;
  • an inner tube 40 provided with feed means (not shown) which allow the introduction into said inner tube 40 of a second flow comprising at least the catalyst of the chemical reaction of step (E) to dispersed state, (with, optionally, the additional reagent (s) necessary to conduct the chemical reaction of step (E) in addition to the reagents present in the first stream), then the flow of this second stream of the inlet 42 of said inner tube to the injection zone 25.
  • the device comprises means for homogenization of the dispersion of the solid catalyst, for example a stirrer (magnetic stirrer or ultrasound in particular).
  • a stirrer magnetic stirrer or ultrasound in particular.
  • the inner tube is a fused silica capillary tube.
  • the nature of the material constituting the outer tube may itself vary to a large extent, provided that it remains compatible with the reagents, catalysts and solvents employed in step (E).
  • the inner tube preferably has an internal diameter greater than 5 times, preferably 10 times, and more preferably 20 times the size of the solid objects formed by the suspended catalyst conveyed in the second stream. Typically, this internal diameter is greater than ⁇ ⁇ , for example between 200 and 800 ⁇ , in particular of the order of ⁇ .
  • the outer tube 30 has, by definition, an inner diameter greater than that of the outer diameter of the inner tube 40. Furthermore, it has an outer diameter less than that of the internal diameter of the flow member 10. Typically, the diameters internal and external outer tube 30 are between 0.5 and 2 mm.
  • the supply means not shown in the Figure and which are used to generate the flow of the carrier liquid phase and the first and second flow (supply means associated with the supply channels 1 1 and 31 and the internal tube 40) are pump-type devices or, more preferably, syringe shoots that allow finer control of the flow.
  • these supply means are used, in a manner known per se, to allow:
  • the formation of the drops at the injection zone 25 by mixing the first and second flows implies that the conditions allowing the reaction of step (E) are not united upstream of this zone 25, which thus fixes the initial time of the reaction in this precise area where the drops are formed.
  • the reaction time within a drop can therefore be directly correlated to its position in the flow member as a function of flow. This phenomenon is referred to as 'space-time equivalence' in this specification.
  • the devices used according to the invention may comprise additional means of regulation and analysis.
  • the flow member may advantageously be provided with means making it possible to thermostate said flow member, or more simply to control its temperature (typically heating means, for example a heated plate etched to the size of the external diameter
  • heating means for example a heated plate etched to the size of the external diameter
  • the temperature control can also be carried out by other techniques, for example by immersing the flow member in a liquid bath or heated sand, by inserting it in an oven, or by wrapping it around a thermostated cylinder.
  • the length of the inner and outer tubes 30 and 40 allowing the injection of the reagents and the catalyst and the formation of the drops can be adapted to ensure a good heating of the temperature. different solutions before the formation of the drops.
  • the parts of the tubes 30 and 40 that are not located inside the flow member may be provided with temperature control means, in particular of the aforementioned type (in particular a heated grooved plate or in a column heater type oven or with a heating tape).
  • the devices used according to the invention advantageously also comprise optical devices for visualizing the flow and the behavior of the catalyst within the drops.
  • optical devices for visualizing the flow and the behavior of the catalyst within the drops.
  • a camera coupled to a microscope, which makes it possible to visualize the flow from above, and another camera with a macro lens. , which simultaneously allows to have a side view. It is thus possible to visualize the flow in three dimensions, which can for example be used to study phenomena such as sedimentation, aggregation, or erosion.
  • the device employed advantageously comprises specific means for to do.
  • the flow member may advantageously be provided with a Raman spectrometric probe, which acquires chemical data on the current reaction.
  • a Raman spectrometric probe has the advantage of being able to be moved along the flow member, which makes it possible to acquire data at different reaction times without modifying the initial flow rates.
  • reaction conditions can be screened by changing one or more operating parameters (composition of the inlet syringes, inflow rates, plate temperature, etc.).
  • the method of the invention also makes it possible, by the reproducibility of the formation of the drops, to integrate the signal on a large number of drops because they have the same history, which increases the statistical quality of the measurements.
  • the signal inherent in the oil can be easily subtracted from the digital processing measurements spectra, allowing to go back to the only composition of the drops and therefore of the reaction medium.
  • the Raman probe described above is given for illustrative purposes.
  • the flow member may also be provided with any other means of non-intrusive analysis (UV-visible spectrometry for example), which allows an online analysis of the medium.
  • reaction medium can also be easily collected at the outlet 13 of the flow member, where it can be easily separated from the oil, for example by simple decantation, possibly separated from the catalyst (by a solid separation / filtration type liquid in particular) then be subjected to any type of analysis (spectrometry, chromatography, titration ...), offline.
  • This off-line analysis technique is particularly interesting when the presence of the solid catalyst disturbs certain spectra obtained online.
  • the device used corresponds to that described in the attached figure, with the following characteristics: - carrier liquid phase: fluorinated IKV-fluorine oil - flow rate: 10 mL / h
  • flow member 10 Teflon-coated capillary tube on its inner surface; internal diameter: 2.2 mm [To be validated]; length: 1 m; thermostated at 80 ° C.
  • 1, 6mm - conveying a first stream: pure anhydride, at a flow rate of 2.5 mL / h
  • - inner tube fused silica capillary with an internal diameter of 500 mm; conveying a second stream: suspension of zeolite USY at 1% in anisole, at a flow rate of 7.5 ml / h
  • composition of the drops was analyzed by Raman spectrometry, which made it possible to calculate the evolution of the yield of the reaction as a function of time from 0 to 20 minutes.
  • data acquisition required only 1.6 mL of anhydride, 5 mL of anisole and 5 mg of catalyst, with a handling time of only 45 minutes.

Abstract

Solid/liquid heterogeneous catalysis in a millifluidic or microfluidic medium. The present invention relates to a process in which a chemical reaction is carried out in a liquid reaction medium in the presence of a solid catalyst, and in which said liquid reaction medium is used in the form of drops carried in a continuous liquid carrier phase which is immiscible with said reaction medium, the flow of which is forced within a tubular flow member having a cross section of which the largest dimension is less than 1 cm, said drops having dimensions less than that of the internal diameter of the flow member; and in which the solid catalyst is used in the dispersed state in said drops. This process is in particular suitable for monitoring the solid/liquid catalysis reaction which takes place in the drops.

Description

Catalyse hétérogène solide/liquide en milieu milli- ou micro-fluidique  Heterogeneous solid / liquid catalysis in milli- or micro-fluidic medium
La présente invention a trait à un procédé mettant en œuvre une réaction employant un catalyseur solide au sein d'un milieu réactionnel liquide hétérogène (ci- après désignée par "catalyse solide/liquide ") et mise en œuvre dans des conditions spécifiques, à savoir au sein de gouttes de taille contrôlées, véhiculées dans un liquide vecteur (phase liquide porteuse continue), au sein d'un réacteur tubulaire de section millimétrique ou micrométrique supérieure à celle des gouttes. Ce procédé particulier, qui met en œuvre la catalyse solide/liquide au sein des gouttes se comportant comme des microréacteurs de taille réduite (typiquement de l'ordre de quelques nanolitres à quelques microlitres) peut, entre autres, être employé pour acquérir des données sur la réaction de catalyse solide/liquide qui s'opère au sein des gouttes, par détermination d'au moins un paramètre physique et/ou chimique du milieu contenu dans les gouttes, ces données s'avérant constituer un excellent reflet de celles qui sont obtenues à une échelle plus macroscopique dans des réacteurs agités de plus grandes dimensions (réacteurs dit "batch" d'un volume bien supérieur à celui des gouttes, d'un volume d'au moins plusieurs centaines de ml_, voire de plusieurs litres, ou plus) mettant en œuvre le même catalyseur solide dispersé au sein du même milieu réactionnel liquide. The present invention relates to a process employing a reaction employing a solid catalyst within a heterogeneous liquid reaction medium (hereinafter referred to as "solid / liquid catalysis") and carried out under specific conditions, namely in controlled size drops, conveyed in a carrier liquid (continuous liquid carrier phase), in a tubular reactor of millimeter or micrometer section greater than that of the drops. This particular method, which implements solid / liquid catalysis within the drops, which behaves as microreactors of reduced size (typically of the order of a few nanoliters to a few microliters) can, among other things, be used to acquire data on the reaction of solid / liquid catalysis that takes place within the drops, by determining at least one physical and / or chemical parameter of the medium contained in the drops, these data proving to be an excellent reflection of those obtained on a more macroscopic scale in larger stirred reactors ("batch" reactors with a volume much greater than that of drops, with a volume of at least several hundred ml, or even several liters, or more ) implementing the same solid catalyst dispersed in the same liquid reaction medium.
De façon générale, les réactions de catalyse solide/liquide présentent un grand intérêt notamment pour l'industrie d'intermédiaires et de spécialités ou de chimie fine, en particulier pour les avantages qu'elle offre en termes de recyclabilité du catalyseur et d'économies dans les étapes de purification des produits finaux. Pour sélectionner au mieux un catalyseur solide bien adapté à une réaction chimique donnée, il est souhaitable d'acquérir le plus de données sur différents catalyseurs (activité chimique du catalyseur, cinétique de la réaction, dégradation du catalyseur...). Typiquement, cette acquisition des données passe par des tests réalisés sur des réacteurs 'batch' agités, qui nécessitent de grandes quantités de matière, ce qui est problématique notamment lorsqu'on souhaite tester des catalyseurs onéreux ou bien lorsqu'on ne dispose que d'un faible échantillon. De plus, les tests demandent souvent à être reproduits plusieurs fois, ce qui se traduit par un temps d'acquisition de données relativement long. Il apparaît donc qu'il existe un besoin d'un système d'acquisition de données qui permettrait de réduire la quantité de catalyseur à employer et la durée nécessaire à l'acquisition. In general, the solid / liquid catalysis reactions are of great interest, particularly for the intermediates and specialty or fine chemicals industry, in particular for the advantages it offers in terms of catalyst recyclability and savings. in the purification steps of the final products. To best select a solid catalyst well suited to a given chemical reaction, it is desirable to acquire the most data on different catalysts (chemical activity of the catalyst, kinetics of the reaction, degradation of the catalyst, etc.). Typically, this acquisition of the data passes by tests carried out on agitated 'batch' reactors, which require large quantities of material, which is problematic in particular when it is desired to test expensive catalysts or else when one only has access to a small sample. In addition, the tests often need to be repeated several times, which results in a relatively long data acquisition time. It therefore appears that there is a need for a data acquisition system that would reduce the amount of catalyst to be used and the time required for acquisition.
Il a été reporté dans la littérature des réactions de catalyse hétérogène mettant en œuvre un catalyseur solide et une phase liquide dans des microréacteurs. A ce sujet, il a essentiellement été décrit l'emploi de catalyseurs solides déposés sur la paroi d'un réacteur de dimension micronique (catalyse en paroi), du type décrit notamment dans Advanced Synthesis and Catalysis, 351 , 3260-3268 (2009), ou bien mettant en œuvre le catalyseur sous la forme d'un lit fixe, comme par exemple dans le Journal of American Chemical Society, 124, 13360-13361 (2002). Heterogeneous catalysis reactions using a solid catalyst and a liquid phase in microreactors have been reported in the literature. In this regard, it has essentially been described the use of solid catalysts deposited on the wall of a reactor of micron dimension (wall catalysis), of the type described in particular in Advanced Synthesis and Catalysis, 351, 3260-3268 (2009). or using the catalyst in the form of a fixed bed, as for example in the Journal of the American Chemical Society, 124, 13360-13361 (2002).
Ces microréacteurs apparaissent séduisants comme outil de modélisation de réaction de catalyse solide/liquide à une plus grande échelle. En effet, compte tenu de leurs faibles dimensions, ils permettent, entre autres, d'opérer la réaction avec une très faible quantité de catalyseur. Néanmoins, les données collectées sur la catalyse hétérogène avec ce type de microréacteurs ne s'avèrent pas directement transposable à un système agité macroscopique. These microreactors appear attractive as a solid / liquid catalysis reaction modeling tool on a larger scale. Indeed, given their small size, they allow, among other things, to operate the reaction with a very small amount of catalyst. Nevertheless, the data collected on heterogeneous catalysis with this type of microreactor do not prove directly transferable to a macroscopic agitated system.
Cette difficulté tient notamment à un comportement particulier lié aux dimensions microniques du réacteur, qui induisent, dans le cas le plus général, des phénomènes de transfert très différents, de ceux d'un système macroscopique agité, et qui s'avèrent parfois limitants, notamment dans le cas de la catalyse en paroi. Par ailleurs, des chemins préférentiels peuvent être observés dans les lits fixes. Enfin, il est noter que, le plus souvent, lorsqu'un catalyseur solide est véhiculé au sein d'un réacteur tubulaire, ce solide est sujet à une dispersion axiale qui entraîne un étalement des temps de séjour effectués dans le réacteur, et donc pénalise la précision des mesures cinétiques effectuées.  This difficulty is due in particular to a particular behavior related to the micronic dimensions of the reactor, which induce, in the most general case, transfer phenomena very different from those of a macroscopic agitated system, and which sometimes prove to be limiting, in particular in the case of wall catalysis. In addition, preferential paths can be observed in fixed beds. Finally, it should be noted that, most often, when a solid catalyst is conveyed within a tubular reactor, this solid is subject to axial dispersion which results in a spreading of the residence times carried out in the reactor, and therefore penalizes the precision of the kinetic measurements made.
Un but de la présente invention est de fournir un réacteur présentant les avantages décrits ci-dessus pour les microréacteurs en paroi et à lit fixe décrits ci- dessus en termes de réduction de la quantité de catalyseur nécessaire pour l'acquisition de données, mais qui permette d'obtenir directement des informations reflétant les propriétés que présente le catalyseur testé lorsque celui-ci est mis en œuvre plus quantitativement dans un réacteur agité. A cet effet, la présente invention propose l'utilisation d'un microréacteur spécifique, mettant en œuvre la réaction de catalyse solide/liquide au sein de gouttes véhiculées dans une phase porteuse liquide au sein d'un organe d'écoulement, typiquement un capillaire ou un canal fluidique. An object of the present invention is to provide a reactor having the advantages described above for the wall and fixed bed microreactors described above in terms of reducing the amount of catalyst needed for data acquisition, but which to obtain directly information reflecting the properties of the catalyst tested when it is implemented more quantitatively in a stirred reactor. For this purpose, the present invention proposes the use of a specific microreactor, implementing the solid / liquid catalysis reaction within drops conveyed in a liquid carrier phase within a flow member, typically a capillary or a fluidic channel.
Plus précisément, la présente invention a pour objet un procédé qui comprend une étape (E) où on réalise une réaction chimique mettant en œuvre au moins un réactif liquide ou solubilisé, au sein d'un milieu réactionnel liquide et en présence d'un catalyseur solide, caractérisé en ce que, dans ladite étape (E):  More specifically, the subject of the present invention is a process which comprises a step (E) in which a chemical reaction is carried out employing at least one liquid or solubilized reagent, in a liquid reaction medium and in the presence of a catalyst. solid, characterized in that, in said step (E):
- ledit milieu réactionnel liquide est mis en œuvre sous la forme de gouttes véhiculées au sein d'une phase liquide porteuse continue, non miscible avec ledit milieu réactionnel, dont on force l'écoulement au sein d'un organe d'écoulement tubulaire ayant une section dont la plus grande dimension est inférieure à 1 cm, de préférence inférieure ou égale à 5 mm, lesdites gouttes ayant des dimensions inférieures à celle du diamètre interne de l'organe d'écoulement ;  said liquid reaction medium is used in the form of drops conveyed within a continuous liquid carrier phase immiscible with said reaction medium, the flow of which is forced through a tubular flow member having a section whose largest dimension is less than 1 cm, preferably less than or equal to 5 mm, said drops having dimensions smaller than that of the internal diameter of the flow member;
- le catalyseur solide est mis en œuvre à l'état dispersé au sein desdites gouttes, de préférence sans présence de catalyseur ailleurs que dans lesdites gouttes.  - The solid catalyst is implemented in the dispersed state within said drops, preferably without the presence of catalyst elsewhere than in said drops.
Typiquement, la section de l'organe d'écoulement dont la plus grande dimension est inférieure à 1 cm, est la section droite de l'organe d'écoulement, typiquement, le diamètre interne de l'organe d'écoulement est intérieur à 1 cm, de préférence inférieure ou égale à 5 mm. Typically, the section of the flow member whose largest dimension is less than 1 cm, is the cross-section of the flow member, typically, the internal diameter of the flow member is inside 1 cm, preferably less than or equal to 5 mm.
Ainsi, selon l'invention, le catalyseur solide est mis en œuvre à l'état dispersé au sein de gouttes nanométriques ou millimétriques jouant, en quelque sorte, le rôle de réacteurs miniaturisés. Les gouttes véhiculées selon l'invention dans l'organe d'écoulement sont de dimension inférieure à celle de la section interne dudit organe d'écoulement et, de préférence, elles ne sont pas en contact avec les parois de l'organe d'écoulement. En d'autres termes, les gouttes sont le plus souvent totalement entourées par la phase liquide porteuse, qui inhibe de ce fait tout effet de bord avec la paroi interne de l'organe d'écoulement. En particulier, les gouttes mises en œuvre selon l'invention, qui sont entourées par une phase liquide porteuse continue, sont à distinguer de 'bouchons' liquides qui serait introduits dans l'organe d'écoulement et qui seraient séparés entre eux par des zones discontinues de phase liquide. Les travaux qui ont été réalisés par les inventeurs dans le cadre de l'invention ont maintenant permis de mettre en évidence que, dans les conditions de mise en œuvre de l'étape (E) ci-dessus, le milieu réactionnel se comporte sensiblement comme il le ferait dans un réacteur agité plus macroscopique. Sur cette base, le procédé de l'invention peut notamment être employé pour déterminer des paramètres de la réaction chimique en présence du catalyseur, ces paramètres étant transposables au comportement du catalyseur dans des réacteurs plus macroscopiques, ce qui permet donc de déterminer efficacement les propriétés d'un catalyseur en n'ayant à en employer qu'une quantité très restreinte. Dans ce cadre, selon un aspect particulier, la présente invention a pour objet le procédé précité, où l'étape (E) comprend, en outre, la mesure d'au moins une caractéristique physique et/ou chimique du milieu solide/liquide contenu dans au moins une des gouttes. Cette mesure peut par exemple être réalisée au moyen d'appareils d'analyse en ligne (sondes spectrométriques par exemple), qui, grâce à l'équivalence espace-temps dans le dispositif de mise en œuvre du procédé de l'invention (décrite plus en détails ci-après), permettent d'avoir en une seule expérience différents points de cinétique chimique. Alternativement, la mesure peut être effectuée au moyen d'analyses hors-ligne, notamment en prélevant un échantillon à la sortie de l'organe d'écoulement. Le procédé de l'invention peut être mis en œuvre avec tout type de catalyseur solide dispersible, par exemple des zéolites, notamment choisi parmi les USY (notamment Y760 et/ou Y720) et/ou Beta ou bien encore des métaux supportés, par exemple sur du charbon (notamment le palladium supporté sur du charbon). Thus, according to the invention, the solid catalyst is implemented in the dispersed state within nanometric or millimetric drops playing, in a way, the role of miniaturized reactors. The drops conveyed according to the invention in the flow member are smaller in size than the internal section of said flow member and, preferably, they are not in contact with the walls of the flow member. . In other words, the drops are most often completely surrounded by the carrier liquid phase, which thereby inhibits any edge effects with the internal wall of the flow member. In particular, the drops implemented according to the invention, which are surrounded by a continuous liquid carrying phase, are to be distinguished from liquid 'plugs' which would be introduced into the flow member and which would be separated from each other by zones discontinuous liquid phase. The work that has been done by the inventors in the context of the invention has now made it possible to demonstrate that, under the conditions of implementation of step (E) above, the reaction medium behaves substantially as it would do it in a stirred reactor more macroscopic. On this basis, the method of the invention can in particular be used to determine parameters of the chemical reaction in the presence of the catalyst, these parameters being transferable to the behavior of the catalyst in more macroscopic reactors, which thus makes it possible to determine the properties of the catalyst. a catalyst by having to use a very limited amount. In this context, in a particular aspect, the present invention relates to the aforementioned method, wherein step (E) further comprises measuring at least one physical and / or chemical characteristic of the solid / liquid medium contained in at least one of the drops. This measurement can for example be carried out by means of on-line analysis devices (spectrometric probes for example), which, thanks to the space-time equivalence in the device for implementing the method of the invention (described more in detail below), allow to have in a single experiment different points of chemical kinetics. Alternatively, the measurement can be carried out by means of off-line analyzes, in particular by taking a sample at the outlet of the flow member. The process of the invention can be carried out with any type of dispersible solid catalyst, for example zeolites, in particular chosen from USYs (especially Y760 and / or Y720) and / or Beta or even supported metals, for example on charcoal (especially palladium supported on charcoal).
Quelle que soit la nature exacte du catalyseur solide employé, il est très aisé d'obtenir la dispersion de ce catalyseur au sein des gouttes, telle qu'elle est recherchée dans l'étape (E). A cet effet, il suffit le plus souvent de forcer l'écoulement au sein de l'organe d'écoulement avec un débit suffisant pour induire la dispersion recherchée. Un accroissement du débit d'écoulement s'accompagne en effet d'une augmentation des mouvements internes au sein des gouttes, liés à la convection forcée par les parois de l'organe d'écoulement, qui suffisent à maintenir le catalyseur en suspension, sensiblement de la même façon qu'il le serait au sein d'un réacteur agité plus macroscopique. Selon un mode de réalisation particulier, le procédé peut éventuellement être conduit en utilisant, en plus de l'écoulement, d'autres moyens additionnels de mise en suspension du catalyseur solide, par exemple en soumettant le milieu réactionnel comprenant le catalyseur à des ultrasons, ou bien encore à un champ magnétique (en utilisant des catalyseurs à caractère magnétique et/ou en rajoutant dans le milieu des particules à caractère magnétique). Le plus souvent, de tels moyens additionnels de mise en suspension du catalyseur solide ne sont pas nécessaires selon l'invention. Whatever the exact nature of the solid catalyst employed, it is very easy to obtain the dispersion of this catalyst in the drops, as sought in step (E). For this purpose, it is most often sufficient to force the flow within the flow member with a flow rate sufficient to induce the desired dispersion. An increase in the flow rate is accompanied by an increase in internal movements within the drops, related to forced convection by the walls of the flow member, which are sufficient to maintain the catalyst in suspension, substantially in the same way that it would be in a stirred reactor more macroscopic. According to a particular embodiment, the process may optionally be conducted using, in addition to the flow, other additional means for suspending the solid catalyst, for example by subjecting the reaction medium comprising the catalyst with ultrasound, or else with a magnetic field (by using catalysts with magnetic character and / or by adding in the medium of the particles with magnetic character). Most often, such additional means for suspending the solid catalyst are not necessary according to the invention.
De préférence, notamment pour obtenir une bonne mise en suspension du catalyseur au sein des gouttes, la phase porteuse liquide employée dans le cadre de la présente invention a une viscosité supérieure à celle du milieu réactionnel liquide des gouttes. Il est cependant préférable que le ratio de la viscosité de la phase porteuse liquide rapporté à celle du milieu réactionnel liquide des gouttes ne soit pas trop élevé, sans quoi il existe des risques, en particulier avec des débits d'écoulement élevés, pour que les interfaces des gouttes se déforment et que des particules de catalyseur soient éjectés hors des gouttes. Typiquement, le ratio de la viscosité de la phase porteuse liquide rapportée à celle du milieu réactionnel liquide des gouttes est compris entre 2 et 1000, de préférence entre 4 et 600, notamment entre 5 et 500, ce rapport étant plus préférentiellement supérieur à 100, et plus avantageusement encore supérieur ou égal à 250, voire à 300, bien qu'il soit également possible de travailler en dehors de ces ratios. Preferably, in particular to obtain a good suspension of the catalyst in the drops, the liquid carrier phase used in the context of the present invention has a viscosity greater than that of the liquid reaction medium of the drops. However, it is preferable that the ratio of the viscosity of the liquid carrier phase to that of the liquid reaction medium drops is not too high, otherwise there are risks, particularly with high flow rates, so that Droplet interfaces deform and catalyst particles are ejected from the drops. Typically, the ratio of the viscosity of the liquid carrier phase relative to that of the liquid reaction medium of the drops is between 2 and 1000, preferably between 4 and 600, in particular between 5 and 500, this ratio being more preferably greater than 100, and more preferably still greater than or equal to 250 or even 300, although it is also possible to work outside these ratios.
Par ailleurs, compte tenu de la mise en œuvre spécifique du catalyseur dans les gouttes dispersées au sein de la phase liquide porteuse, l'étape (E), malgré son caractère miniaturisé, ne conduit pas à une dispersion axiale du solide, dans la mesure où celui-ci s'écoule avec les gouttes et est donc entraînés "d'un seul bloc" dans le courant de la phase porteuse liquide. Par ailleurs, le procédé de l'invention n'est pas non plus sujet aux phénomènes de transfert qui sont observés avec la catalyse en paroi de l'état de la technique, ni à la présence de chemins préférentiels comme dans le cas de catalyseurs employés en lit fixe. Moreover, in view of the specific implementation of the catalyst in the drops dispersed within the carrier liquid phase, step (E), despite its miniaturized nature, does not lead to an axial dispersion of the solid, as far as where it flows with the drops and is thus driven "in one block" in the current of the liquid carrier phase. Furthermore, the method of the invention is not subject to the transfer phenomena that are observed with the prior art wall catalysis, nor to the presence of preferential paths as in the case of catalysts employed. in fixed bed.
Selon un mode de réalisation particulièrement avantageux de l'étape (E), les gouttes sont formées en continu au sein de la phase liquide porteuse. Typiquement, les gouttes sont formées en injectant de façon séquentielle ou continue le milieu réactionnel liquide contenant les particules (ou, plus avantageusement, en co- injectant de façon séquentielle ou continue plusieurs flux séparés dont le mélange forme le milieu réactionnel liquide contenant les particules), au sein d'un flux continu de phase liquide porteuse véhiculée au sein de l'organe d'écoulement. Lorsque l'injection (ou la co-injection de plusieurs flux) est réalisée de façon continue, les gouttes sont obtenues en employant des débits adaptés, selon une méthode bien connue en soi, décrite par exemple dans la demande FR 2 907 030. Ce mode de réalisation permet notamment de contrôler la taille et la vitesse de gouttes. De préférence l'injection au sein du flux continu de phase liquide porteuse est opérée au moyen d'un système d'injection débouchant au cœur de l'organe d'écoulement, ce qui permet d'obtenir des particules non au contact des parois de l'organe d'écoulement. According to a particularly advantageous embodiment of step (E), the drops are formed continuously within the carrier liquid phase. Typically, the drops are formed by sequentially or continuously injecting the liquid reaction medium containing the particles (or, more advantageously, by sequentially or continuously co-injecting several separate streams, the mixture of which forms the liquid reaction medium containing the particles). , within a continuous flow of liquid carrier phase conveyed within the flow member. When the injection (or the co-injection of several streams) is carried out continuously, the drops are obtained by using suitable flow rates, according to a method well known per se, described for example in the application FR 2 907 030. This embodiment allows in particular to control the size and speed of drops. Preferably, the injection into the continuous stream of liquid carrier phase is carried out by means of an injection system opening into the heart of the flow member, which makes it possible to obtain particles that are not in contact with the walls of the the flow member.
Par ailleurs, les réactifs et catalyseur sont de préférence introduits de façon séparée, de sorte que leur mise en contact ne s'opère qu'au moment de la formation de la goutte, ce qui permet de déterminer le temps initial où débute la réaction. Pour ce faire, on peut typiquement co-injecter de façon séquentielle ou continue : Furthermore, the reagents and catalyst are preferably introduced separately, so that they come into contact only at the time of formation of the drop, which allows to determine the initial time when the reaction begins. To do this, one can typically co-inject sequentially or continuously:
- un premier flux d'introduction comprenant au moins un réactif mis en œuvre dans la réaction chimique de l'étape (E), à l'état liquide ou solubilisé, ledit premier flux ne comprenant pas de catalyseur ; et a first feed stream comprising at least one reagent used in the chemical reaction of step (E), in the liquid or solubilized state, said first stream comprising no catalyst; and
- un deuxième flux d'introduction distinct du premier, comprenant le catalyseur. Selon ce mode de réalisation, le deuxième flux d'introduction contenant le catalyseur est, le plus souvent constitué du catalyseur dispersé au sein d'un milieu dispersant ou bien il comprend le catalyseur à l'état dispersé et un ou plusieurs réactif(s) distinct(s) du (ou des) réactif(s) présent(s) dans le premier flux d'introduction. On peut éventuellement co-injecter un ou plusieurs flux en plus des deux flux décrits ci-dessus, par exemple un troisième flux comprenant un réactif autre que celui du premier flux. a second introduction stream distinct from the first, comprising the catalyst. According to this embodiment, the second feed stream containing the catalyst is most often constituted by the dispersed catalyst in a dispersing medium or it comprises the catalyst in the dispersed state and one or more reagent (s) distinct (s) of the reagent (s) present in the first introduction stream. One or more streams may optionally be co-injected in addition to the two flows described above, for example a third stream comprising a reagent other than that of the first stream.
Selon un mode de réalisation préférentiel de l'étape (E), adapté à une mise en œuvre selon un mode continu, les gouttes de milieu réactionnel sont formées au sein de l'organe d'écoulement au moyen d'un système d'injection débouchant au sein dudit organe d'écoulement et comprenant deux canalisations tubulaires, à savoir : According to a preferred embodiment of step (E), suitable for implementation in a continuous mode, the drops of reaction medium are formed within the flow member by means of an injection system opening into said flow member and comprising two tubular pipes, namely:
une première canalisation tubulaire (désignée ci-après par 'tube externe') véhiculant un premier flux comprenant au moins un réactif, liquide ou solubilisé, mis en œuvre dans la réaction de l'étape (E) ; et  a first tubular pipe (hereinafter referred to as an "outer tube") conveying a first stream comprising at least one reagent, liquid or solubilized, used in the reaction of step (E); and
- une deuxième canalisation tubulaire (désignée ci-après par 'tube interne'), localisée au sein de ladite première canalisation tubulaire (typiquement, le tube interne et le tube externe sont coaxiaux) et véhiculant un deuxième flux comprenant le catalyseur à l'état dispersé, et éventuellement un ou plusieurs réactif(s) distinct(s) du (ou des) réactif(s) présent(s) dans le premier flux d'introduction. Ce tube interne a de préférence un diamètre interne supérieur ou égal à 5 fois (de préférence supérieur ou égal à 10 fois, et plus préférentiellement supérieur ou égal à 20 fois) la taille des objets solidesa second tubular duct (hereinafter referred to as an "inner tube") located in said first tubular duct (typically, the inner tube and the outer tube are coaxial) and conveying a second stream comprising the catalyst in the dispersed state, and optionally one or more reagent (s) distinct (s) reagent (s) present (s) in the first feed stream. This inner tube preferably has an internal diameter greater than or equal to 5 times (preferably greater than or equal to 10 times, and more preferably greater than or equal to 20 times) the size of the solid objects
(particules individualisés, agrégats de particules ou agglomérats, notamment, dont la taille dans les gouttes peut par exemple être mesurée par diffusion de la lumière) formés par le catalyseur en suspension véhiculé dans le deuxième flux, et ce notamment de façon à inhiber des phénomènes de bouchage par le catalyseur solide. Typiquement le diamètre interne du tube interne est d'au moins 100 micromètres, de préférence d'au moins 200 micromètres (par exemple de l'ordre de 500 microns). (Individualized particles, aggregates of particles or agglomerates, in particular, whose size in the drops may for example be measured by light scattering) formed by the suspended catalyst conveyed in the second stream, and in particular so as to inhibit capping by the solid catalyst. Typically the internal diameter of the inner tube is at least 100 microns, preferably at least 200 microns (for example of the order of 500 microns).
Une conduite du procédé de l'invention selon le mode continu précité autorise par ailleurs un changement rapide des paramètres opératoires en cours d'acquisition de données relative à la réaction chimique et au catalyseur étudiés, ce qui permet d'acquérir des informations différentes sans avoir pour ce faire à arrêter le procédé. En fait, schématiquement, chaque goutte véhiculée dans l'organe d'écoulement se comporte comme un réacteur individuel où les conditions opératoire peuvent varier par rapport à une goutte voisine, ce qui permet des comparaisons directes dans strictement les mêmes conditions de température et de pression. Cette possibilité de mesures multiples et de comparaison directe représente encore un autre avantage très intéressant du procédé de l'invention, notamment par rapport aux procédés mis en œuvre à plus grande échelle. A conduct of the method of the invention according to the aforementioned continuous mode also authorizes a rapid change of the operating parameters during data acquisition relating to the chemical reaction and to the catalyst studied, which makes it possible to acquire different information without having to do this to stop the process. In fact, schematically, each drop conveyed in the flow member behaves like an individual reactor where the operating conditions can vary with respect to a neighboring drop, which allows direct comparisons in strictly the same conditions of temperature and pressure . This possibility of multiple measurements and direct comparison represents yet another very interesting advantage of the method of the invention, especially with respect to the processes implemented on a larger scale.
Le procédé de l'invention présent par ailleurs l'avantage d'être très modulable, aussi bien en termes de nature de catalyseur, réactifs et phases liquides, qu'en ce qui concerne les conditions opératoires. The process of the invention also has the advantage of being very flexible, both in terms of the nature of the catalyst, the reactants and the liquid phases, as well as with regard to the operating conditions.
De préférence, la phase liquide porteuse est inerte vis-à-vis de la réaction chimique. Cela étant, hormis cette condition (et le fait que la phase liquide porteuse doit être non miscible avec le milieu réactionnel liquide des gouttes), le catalyseur, les réactifs mis en œuvre dans la réaction chimique et les différentes phases liquides en présence dans l'étape (E) peuvent varier en une très large mesure. En particulier, les réactifs et solvants éventuels de la phase organique peuvent être aussi bien hydrophiles qu'hydrophobes. Selon un mode de réalisation intéressant, compatible avec la plupart des réactions de catalyse solide/liquide qui peuvent être étudiées selon l'invention, la phase liquide porteuse est une huile fluorée, notamment de type de l'huile commercialisée sous le nom de IKV-fluor par la société IKV tribologie. Notamment dans ce cas, il est particulièrement intéressant que la paroi interne de l'organe d'écoulement comprenne, au moins en surface, un matériau organique fluoré, par exemple de type Téflon. Preferably, the carrier liquid phase is inert with respect to the chemical reaction. That being the case, apart from this condition (and the fact that the carrier liquid phase must be immiscible with the liquid reaction medium of the drops), the catalyst, the reagents used in the chemical reaction and the different liquid phases present in the step (E) can vary to a very large extent. In particular, the reactants and optional solvents of the organic phase can be both hydrophilic and hydrophobic. According to an interesting embodiment, compatible with most of the solid / liquid catalysis reactions that can be studied according to the invention, the carrier liquid phase is a fluorinated oil, in particular of the type of the oil marketed under the name of IKV. fluorine by the company IKV tribology. In this case, it is particularly interesting that the internal wall of the flow member comprises, at least on the surface, a fluorinated organic material, for example of the Teflon type.
Selon une autre variante envisageable, adaptée notamment lorsque la phase liquide des gouttes est de type hydrophile (aqueuse notamment), la phase liquide porteuse peut être une huile siliconée. According to another conceivable variant, adapted in particular when the liquid phase of the drops is of hydrophilic type (aqueous in particular), the carrier liquid phase may be a silicone oil.
Par ailleurs, l'étape (E) peut être mise en œuvre dans une large gamme de pressions et de températures. Typiquement l'étape (E) peut être conduite à des pressions pouvant aller de 1 à 30 bars, typiquement sous pression, à une pression de préférence inférieure ou égale à 20 bars, typiquement entre 1 ,5 et 10 bars. Par ailleurs, l'étape (E) peut être mise en œuvre à des températures pouvant aller jusqu'à 200°C, par exemple entre 10 et 150°C. Furthermore, step (E) can be implemented in a wide range of pressures and temperatures. Typically, step (E) can be carried out at pressures ranging from 1 to 30 bars, typically under pressure, at a pressure preferably of less than or equal to 20 bars, typically between 1.5 and 10 bars. Furthermore, step (E) may be carried out at temperatures up to 200 ° C, for example between 10 and 150 ° C.
Différentes caractéristiques préférentielles et avantages du procédé vont maintenant être décrits plus en détails en référence à la Figure ci-annexée et à l'exemple de réalisation donné ci-après. Various preferred features and advantages of the process will now be described in more detail with reference to the attached figure and the embodiment given below.
La Figure ci-annexée est une représentation schématique en coupe d'un dispositif 1 permettant la mise en œuvre du procédé de l'invention, dit 'milliréacteur'. The attached figure is a schematic representation in section of a device 1 for implementing the method of the invention, said millireactor.
Ce dispositif comprend un organe d'écoulement 10, représentatif des organes d'écoulement utilisables selon l'invention. Il s'agit sur la figure d'un tube cylindrique, de type capillaire, mais d'autres organes tubulaires pourraient être utilisés. Dans le cas le plus général, l'organe d'écoulement utilisé selon l'invention a une section dont la plus grande dimension est inférieure à 1 cm, de préférence inférieure à 5 mm, par exemple entre 0,5 et 4 mm. Notamment lorsqu'il s'agit d'un tube cylindrique tel que représenté sur la Figure, son diamètre interne est typiquement compris entre 1 et 3 mm. L'organe d'écoulement mis en œuvre selon l'invention (par exemple l'organe 10 de la Figure) présente avantageusement un caractère transparent sur tout ou partie de sa longueur, ce qui permet notamment une observation de l'écoulement qui y a lieu et du comportement au sein des gouttes. This device comprises a flow member 10, representative of the flow members that can be used according to the invention. It is in the form of a cylindrical tube, capillary type, but other tubular members could be used. In the most general case, the flow member used according to the invention has a section whose largest dimension is less than 1 cm, preferably less than 5 mm, for example between 0.5 and 4 mm. In particular when it is a cylindrical tube as shown in the Figure, its internal diameter is typically between 1 and 3 mm. The flow member implemented according to the invention (for example the member 10 of the Figure) advantageously has a transparent character on all or part of its length, which allows in particular an observation of the flow that takes place and the behavior within the drops.
Lorsqu'on souhaite mettre en œuvre la mesure d'au moins une caractéristique physique et/ou chimique du milieu solide/liquide contenu dans au moins une des gouttes lors de l'étape (E), il est préférable d'aménager au moins une fenêtre dans un matériau à caractère transparent sur l'organe d'écoulement, au travers de laquelle l'observation est réalisable. Selon un mode de réalisation avantageux, l'organe d'écoulement est entièrement constitué par un matériau à caractère transparent. Par 'caractère transparent', on entend ici, au sens large, que l'organe d'écoulement est formé par un ou plusieurs matériaux dont la nature physico-chimique permet l'observation et/ou la mesure recherchée et ne constitue pas un écran total à cette observation et/ou cette mesure. Il ne s'agit donc pas nécessairement d'une transparence optique, ni d'une transparence totale.  When it is desired to implement the measurement of at least one physical and / or chemical characteristic of the solid / liquid medium contained in at least one of the drops during step (E), it is preferable to arrange at least one window in a transparent material on the flow member, through which the observation is feasible. According to an advantageous embodiment, the flow member is entirely constituted by a transparent material. By "transparent character" is meant here, in the broad sense, that the flow member is formed by one or more materials whose physico-chemical nature allows the observation and / or the desired measurement and does not constitute a screen total to this observation and / or this measurement. It is not necessarily an optical transparency, nor a total transparency.
L'organe d'écoulement mis en œuvre selon l'invention peut typiquement être un tube en matière plastique tel que le PTFE ou le PFA. De préférence, quelle que soit sa nature, sa surface interne comprend de préférence, au moins en surface, un polymère organique fluoré tel que le Téflon.  The flow member implemented according to the invention may typically be a plastic tube such as PTFE or PFA. Preferably, whatever its nature, its internal surface preferably comprises, at least on the surface, a fluorinated organic polymer such as Teflon.
La longueur de l'organe d'écoulement mis en œuvre selon l'invention peut varier en une assez large mesure. A ce sujet, les inventeurs ont mis en lumière que l'écoulement au sein de cet organe d'écoulement reste généralement stable y compris pour de très grandes longueurs. Typiquement, notamment lorsque l'organe d'écoulement est un tube cylindrique de type capillaire tel que représenté sur la Figure, il peut avoir une longueur comprise entre 0,5 et 10 mètres, notamment entre 1 et 3 mètres, sachant que l'écoulement reste stable pour des dimensions plus élevées.  The length of the flow member implemented according to the invention can vary to a large extent. In this regard, the inventors have highlighted that the flow within this flow member remains generally stable even for very long lengths. Typically, especially when the flow member is a cylindrical tube of the capillary type as shown in the Figure, it may have a length of between 0.5 and 10 meters, in particular between 1 and 3 meters, knowing that the flow remains stable for larger dimensions.
L'organe d'écoulement 10 représenté sur la Figure est muni d'un canal d'alimentation 1 1 muni de moyen d'amenée (non représentés) qui permettent l'introduction dans l'organe d'écoulement d'une phase liquide porteuse puis son écoulement de l'entrée 12 dudit organe vers sa sortie 13.  The flow member 10 shown in the Figure is provided with a feed channel 1 1 provided with feed means (not shown) which allow the introduction into the flow member of a carrier liquid phase then its flow from the inlet 12 of said member to its outlet 13.
D'autre part, l'organe d'écoulement 10 est muni d'un système d'injection 20 débouchant au niveau d'une zone d'injection 25 localisée au sein de l'espace interne de l'organe d'écoulement où a lieu l'écoulement de la phase liquide porteuse. Sur le mode de réalisation représenté sur la Figure, qui correspond à un mode de réalisation préférentiel de l'invention, ce système d'injection 20 comprend deux tubes, à savoir : - un tube externe 30, muni d'un canal d'alimentation 31 muni de moyen d'amenée (non représentés) qui permettent l'introduction dans ledit tube externe 30 d'un premier flux comprenant au moins un réactif mis en œuvre dans la réaction chimique de l'étape (E) et ne comprenant pas de catalyseur, puis son écoulement de l'entrée 32 dudit tube externe vers la zone d'injection 25 ; On the other hand, the flow member 10 is provided with an injection system 20 opening at an injection zone 25 located within the internal space of the flow member where a the flow of the carrier liquid phase. In the embodiment shown in the Figure, which corresponds to a preferred embodiment of the invention, this injection system comprises two tubes, namely: an outer tube 30, provided with a supply channel 31 provided with feed means (not shown) which allow the introduction into said outer tube 30 of a first flow comprising at least one reagent implemented in the chemical reaction of step (E) and not comprising a catalyst, then its flow from the inlet 32 of said outer tube to the injection zone 25;
- un tube interne 40, muni de moyen d'amenée (non représentés) qui permettent l'introduction dans ledit tube interne 40 d'un deuxième flux comprenant au moins le catalyseur de la réaction chimique de l'étape (E) à l'état dispersé, (avec, éventuellement le ou les réactif(s) additionnels nécessaires pour conduire la réaction chimique de l'étape (E) en complément des réactifs présents dans le premier flux), puis l'écoulement de ce second flux de l'entrée 42 dudit tube interne vers la zone d'injection 25.  an inner tube 40, provided with feed means (not shown) which allow the introduction into said inner tube 40 of a second flow comprising at least the catalyst of the chemical reaction of step (E) to dispersed state, (with, optionally, the additional reagent (s) necessary to conduct the chemical reaction of step (E) in addition to the reagents present in the first stream), then the flow of this second stream of the inlet 42 of said inner tube to the injection zone 25.
De préférence, en aval de l'entrée du tube interne 40, le dispositif comprend des moyens permettant une homogénéisation de la dispersion du catalyseur solide, par exemple un agitateur (agitateur magnétique ou ultrasons notamment).  Preferably, downstream of the inlet of the inner tube 40, the device comprises means for homogenization of the dispersion of the solid catalyst, for example a stirrer (magnetic stirrer or ultrasound in particular).
Typiquement, le tube interne est un tube capillaire en silice fondue. La nature du matériau constitutif du tube externe peut, elle, varier en une large mesure, à condition qu'elle reste compatible avec les réactifs, catalyseurs et solvants employés dans l'étape (E).  Typically, the inner tube is a fused silica capillary tube. The nature of the material constituting the outer tube may itself vary to a large extent, provided that it remains compatible with the reagents, catalysts and solvents employed in step (E).
Le tube interne a de préférence un diamètre interne supérieur à 5 fois, de préférence à 10 fois, et plus préférentiellement à 20 fois la taille des objets solides formés par le catalyseur en suspension véhiculé dans le deuxième flux. Typiquement, ce diamètre interne est supérieur à Ι ΟΟμηη, par exemple entre 200 et 800 μηη, notamment de l'ordre de δθθμηι. Le tube externe 30 a, par définition, un diamètre interne supérieur à celui du diamètre externe du tube interne 40. Par ailleurs, il a un diamètre externe inférieur à celui du diamètre interne de l'organe d'écoulement 10. Typiquement, les diamètres internes et externes du tube externe 30 sont compris entre 0,5 et 2 mm.  The inner tube preferably has an internal diameter greater than 5 times, preferably 10 times, and more preferably 20 times the size of the solid objects formed by the suspended catalyst conveyed in the second stream. Typically, this internal diameter is greater than Ι ΟΟμηη, for example between 200 and 800 μηη, in particular of the order of δθθμηι. The outer tube 30 has, by definition, an inner diameter greater than that of the outer diameter of the inner tube 40. Furthermore, it has an outer diameter less than that of the internal diameter of the flow member 10. Typically, the diameters internal and external outer tube 30 are between 0.5 and 2 mm.
Typiquement, les moyens d'amenée, non représentés sur la Figure et qui sont employés pour engendrer l'écoulement de la phase liquide porteuse et des premier et deuxième flux (moyens d'amenée associés aux canaux d'alimentation 1 1 et 31 et au tube interne 40) sont des dispositifs de type pompe ou, plus avantageusement, des pousses seringues qui permettent un contrôle plus fin de l'écoulement. Lors de la mise en œuvre de l'étape (E) selon l'invention, ces moyens d'amenée sont employés, de façon connue en soi, pour permettre : Typically, the supply means, not shown in the Figure and which are used to generate the flow of the carrier liquid phase and the first and second flow (supply means associated with the supply channels 1 1 and 31 and the internal tube 40) are pump-type devices or, more preferably, syringe shoots that allow finer control of the flow. When implementation of step (E) according to the invention, these supply means are used, in a manner known per se, to allow:
- un écoulement continu de la phase liquide porteuse au sein de l'organe d'écoulement ; et  a continuous flow of the carrier liquid phase within the flow member; and
- un écoulement simultané des premier et deuxième flux, qui permet d'engendrer des gouttes 50 de milieu réactionnel au sein de la phase liquide porteuse mise en écoulement dans l'organe d'écoulement 10. Cet écoulement peut être réalisé soit de façon séquentielle, soit de façon continue (en adaptant les débits dans le cas d'un mode continu de façon à obtenir les gouttes recherchées). La dispersion du catalyseur au sein des gouttes est obtenue en faisant s'écouler la phase liquide porteuse avec un débit suffisamment élevé pour induire une convection forcée par les parois de l'organe d'écoulement.  a simultaneous flow of the first and second flows, which makes it possible to generate drops of reaction medium within the carrier liquid phase placed in flow in the flow member 10. This flow can be carried out either sequentially, either continuously (by adapting the flow rates in the case of a continuous mode so as to obtain the desired drops). The dispersion of the catalyst in the drops is obtained by flowing the carrier liquid phase with a sufficiently high flow rate to induce forced convection by the walls of the flow member.
La formation des gouttes au niveau de la zone d'injection 25 par mélange des premier et deuxième flux implique que les conditions permettant la réaction de l'étape (E) ne sont pas réunies en amont de cette zone 25, ce qui fixe ainsi le temps initial de la réaction dans cette zone précise où les gouttes sont formées. La durée de réaction au sein d'une goutte peut dès lors être directement corrélée à sa position dans l'organe d'écoulement en fonction du débit. Ce phénomène est désigné par 'équivalence espace-temps' dans la présente description. The formation of the drops at the injection zone 25 by mixing the first and second flows implies that the conditions allowing the reaction of step (E) are not united upstream of this zone 25, which thus fixes the initial time of the reaction in this precise area where the drops are formed. The reaction time within a drop can therefore be directly correlated to its position in the flow member as a function of flow. This phenomenon is referred to as 'space-time equivalence' in this specification.
Les dispositifs employés selon l'invention, notamment ceux du type représentés sur la Figure, peuvent comprendre des moyens additionnels de régulation et d'analyse. The devices used according to the invention, in particular those of the type shown in the Figure, may comprise additional means of regulation and analysis.
En particulier, l'organe d'écoulement peut avantageusement être muni de moyens permettant de thermostater ledit organe d'écoulement, ou plus simplement de contrôler sa température (typiquement des moyens de chauffage, par exemple une plaque chauffée gravée à la dimension du diamètre externe de l'organe d'écoulement, qui permet de contrôler la température sur une grande longueur. Le contrôle de la température peut aussi être effectué par d'autres techniques, par exemples en plongeant l'organe d'écoulement dans un bain liquide ou du sable chauffé, en l'insérant dans un four, ou bien encore en l'enroulant autour d'un cylindre thermostaté. S'agissant du contrôle de la température, il est également à noter que la longueur des tubes interne et externe 30 et 40 permettant l'injection des réactifs et du catalyseur et la formation des gouttes peut être adaptée pour assurer une bonne mise en température des différentes solutions avant la formation des gouttes. En particulier, les parties des tubes 30 et 40 qui ne sont pas situés à l'intérieur de l'organe d'écoulement peuvent être munies de moyens de contrôle de la température, notamment du type précité (notamment une plaque chauffée rainurée ou dans un four type chauffe-colonne ou à l'aide d'un ruban chauffant). In particular, the flow member may advantageously be provided with means making it possible to thermostate said flow member, or more simply to control its temperature (typically heating means, for example a heated plate etched to the size of the external diameter The temperature control can also be carried out by other techniques, for example by immersing the flow member in a liquid bath or heated sand, by inserting it in an oven, or by wrapping it around a thermostated cylinder. As regards the temperature control, it should also be noted that the length of the inner and outer tubes 30 and 40 allowing the injection of the reagents and the catalyst and the formation of the drops can be adapted to ensure a good heating of the temperature. different solutions before the formation of the drops. In particular, the parts of the tubes 30 and 40 that are not located inside the flow member may be provided with temperature control means, in particular of the aforementioned type (in particular a heated grooved plate or in a column heater type oven or with a heating tape).
Par ailleurs, les dispositifs employés selon l'invention comportent avantageusement, en outre, des dispositifs optiques permettant de visualiser l'écoulement et le comportement du catalyseur au sein des gouttes. Par exemple, dans le cas d'un dispositif tel que représenté sur la Figure ci-jointe, on peut employer par exemple une caméra couplée à un microscope, qui permet de visualiser l'écoulement de dessus, et une autre caméra avec un objectif macro, qui permet simultanément d'avoir une vue de côté. Il est ainsi possible de visualiser l'écoulement en trois dimensions, ce qui peut par exemple être mis à profit pour étudier des phénomènes tels que la sédimentation, l'agrégation, ou l'érosion. Furthermore, the devices used according to the invention advantageously also comprise optical devices for visualizing the flow and the behavior of the catalyst within the drops. For example, in the case of a device as shown in the attached figure, it is possible to use, for example, a camera coupled to a microscope, which makes it possible to visualize the flow from above, and another camera with a macro lens. , which simultaneously allows to have a side view. It is thus possible to visualize the flow in three dimensions, which can for example be used to study phenomena such as sedimentation, aggregation, or erosion.
Lorsqu'on souhaite mettre en œuvre la mesure d'au moins une caractéristique physique et/ou chimique du milieu solide/liquide contenu dans au moins une des gouttes lors de l'étape (E), le dispositif employé comporte avantageusement des moyens spécifiques pour ce faire.  When it is desired to implement the measurement of at least one physical and / or chemical characteristic of the solid / liquid medium contained in at least one of the drops during step (E), the device employed advantageously comprises specific means for to do.
Par exemple, l'organe d'écoulement peut avantageusement être muni d'une sonde spectrométrique Raman, qui d'acquérir des données chimiques sur la réaction en cours. Une telle sonde présente l'avantage de pouvoir être déplacée le long de l'organe d'écoulement, ce qui permet d'acquérir des données à différents temps de réaction sans modifier les débits initiaux.  For example, the flow member may advantageously be provided with a Raman spectrometric probe, which acquires chemical data on the current reaction. Such a probe has the advantage of being able to be moved along the flow member, which makes it possible to acquire data at different reaction times without modifying the initial flow rates.
Alternativement, si la sonde est placée et un point fixe, différentes conditions réactionnelles peuvent être criblées en changeant un ou des paramètres opératoires (composition des seringues d'entrée, débits entrants, température de la plaque, notamment).  Alternatively, if the probe is placed and a fixed point, different reaction conditions can be screened by changing one or more operating parameters (composition of the inlet syringes, inflow rates, plate temperature, etc.).
Le procédé de l'invention permet en outre, de par la reproductibilité de la formation des gouttes, d'intégrer le signal sur un grand nombre de gouttes car elles ont la même histoire, ce qui augmente la qualité statistique des mesures. Le signal inhérent à l'huile peut être aisément soustrait des mesures par traitement numérique des spectres, permettant de remonter à la seule composition des gouttes et donc du milieu réactionnel. The method of the invention also makes it possible, by the reproducibility of the formation of the drops, to integrate the signal on a large number of drops because they have the same history, which increases the statistical quality of the measurements. The signal inherent in the oil can be easily subtracted from the digital processing measurements spectra, allowing to go back to the only composition of the drops and therefore of the reaction medium.
La sonde Raman décrite ci-dessus est donnée à titre illustratif. L'organe d'écoulement peut également être muni de tout autres moyens d'analyse non intrusive (spectrométrie UV-visible par exemple), qui permet une analyse en ligne du milieu.  The Raman probe described above is given for illustrative purposes. The flow member may also be provided with any other means of non-intrusive analysis (UV-visible spectrometry for example), which allows an online analysis of the medium.
Par ailleurs, le milieu réactionnel peut également être facilement recueilli à la sortie 13 de l'organe d'écoulement, où il peut être aisément séparé de l'huile, par exemple par simple décantation, éventuellement être séparé du catalyseur (par une séparation solide/liquide de type filtration notamment) puis être soumis à tout type d'analyse (spectrométrie, chromatographie, titration...), hors ligne.  Moreover, the reaction medium can also be easily collected at the outlet 13 of the flow member, where it can be easily separated from the oil, for example by simple decantation, possibly separated from the catalyst (by a solid separation / filtration type liquid in particular) then be subjected to any type of analysis (spectrometry, chromatography, titration ...), offline.
Cette technique d'analyse hors ligne s'avère notamment intéressante lorsque la présence du catalyseur solide perturbe certains spectres obtenus en ligne.  This off-line analysis technique is particularly interesting when the presence of the solid catalyst disturbs certain spectra obtained online.
Certains avantages et caractéristiques de l'invention sont illustrés dans l'exemple plus précis donné ci-après. Certain advantages and features of the invention are illustrated in the more specific example given below.
EXEMPLE : acylation de l'anisole catalysée par une zéolite EXAMPLE: Acylation of anisole catalyzed by a zeolite
A des fins illustrative, la cinétique de la réaction d'acylation de l'anisole catalysée par une zéolite (USY : zéolite de type Y). La zéolite Y760 a été testée dans l'exemple ci-après et la réaction avec une zéolite Y720 permet d'obtenir des résultats similaires. La réaction étudiée est la suivante :
Figure imgf000015_0001
For illustrative purposes, the kinetics of the anisole acylation reaction catalyzed by a zeolite (USY: Y-type zeolite). The zeolite Y760 was tested in the example below and the reaction with zeolite Y720 provides similar results. The reaction studied is as follows:
Figure imgf000015_0001
Le dispositif employé correspond à celui décrit sur la Figure ci-jointe, avec les caractéristiques ci-après : - phase liquide porteuse : huile fluorée IKV-fluor - débit : 10 mL/h The device used corresponds to that described in the attached figure, with the following characteristics: - carrier liquid phase: fluorinated IKV-fluorine oil - flow rate: 10 mL / h
- organe d'écoulement 10 : tube capillaire recouvert de téflon sur sa surface interne ; diamètre interne : 2,2 mm [A valider] ; longueur : 1 m ; thermostaté à 80°C.  flow member 10: Teflon-coated capillary tube on its inner surface; internal diameter: 2.2 mm [To be validated]; length: 1 m; thermostated at 80 ° C.
- tube externe : tube en PFA diamètre interne : 1 mm ; diamètre externe :  - outer tube: PFA tube internal diameter: 1 mm; outer diameter:
1 ,6mm - véhiculant un premier flux : anhydride pur, à un débit de 2,5 mL/h 1, 6mm - conveying a first stream: pure anhydride, at a flow rate of 2.5 mL / h
- tube interne : capillaire de silice fondue d'un diamètre interne de 500 mm ; véhiculant un deuxième flux : suspension de zéolite USY à 1 % dans l'anisole, à un débit de 7,5 mL/h - inner tube: fused silica capillary with an internal diameter of 500 mm; conveying a second stream: suspension of zeolite USY at 1% in anisole, at a flow rate of 7.5 ml / h
La composition des gouttes a été analysée par spectrométrie Raman, ce qui a permis de calculer l'évolution du rendement de la réaction en fonction du temps de 0 à 20 minutes. Au total, l'acquisition des données n'a nécessité que 1 ,6 mL d'anhydride, 5 mL d'anisole et 5 mg de catalyseur, avec un temps de manipulation de 45 minutes seulement. The composition of the drops was analyzed by Raman spectrometry, which made it possible to calculate the evolution of the yield of the reaction as a function of time from 0 to 20 minutes. In total, data acquisition required only 1.6 mL of anhydride, 5 mL of anisole and 5 mg of catalyst, with a handling time of only 45 minutes.
Les résultats obtenus sont parfaitement en ligne avec ceux obtenus pour un réacteur de type "batch" agité macroscopique.  The results obtained are perfectly in line with those obtained for a stirred macroscopic batch reactor.

Claims

REVENDICATIONS
1. - Procédé comprenant une étape (E) où on réalise une réaction chimique mettant en œuvre au moins un réactif liquide ou solubilisé, au sein d'un milieu réactionnel liquide et en présence d'un catalyseur solide, caractérisé en ce que, dans ladite étape (E) : 1. - Process comprising a step (E) in which a chemical reaction is carried out employing at least one liquid or solubilized reagent, in a liquid reaction medium and in the presence of a solid catalyst, characterized in that, in said step (E):
- ledit milieu réactionnel liquide est mis en œuvre sous la forme de gouttes véhiculées au sein d'une phase liquide porteuse continue, non miscible avec ledit milieu réactionnel, dont on force l'écoulement au sein d'un organe d'écoulement tubulaire ayant une section dont la plus grande dimension est inférieure à 1 cm, de préférence inférieure ou égale à 5 mm, lesdites gouttes ayant des dimensions inférieures à celle du diamètre interne de Γ organe d'écoulement ;  said liquid reaction medium is used in the form of drops conveyed within a continuous liquid carrier phase immiscible with said reaction medium, the flow of which is forced through a tubular flow member having a section whose largest dimension is less than 1 cm, preferably less than or equal to 5 mm, said drops having dimensions smaller than that of the internal diameter of the flow member;
- le catalyseur solide est mis en œuvre à l'état dispersé au sein desdites gouttes.  - The solid catalyst is implemented in the dispersed state within said drops.
2. - Procédé selon la revendication 1 , où l'étape (E) comprend en outre la mesure d'au moins une caractéristique physique et/ou chimique du milieu solide/liquide contenu dans au moins une des gouttes. 2. - The method of claim 1, wherein step (E) further comprises measuring at least one physical and / or chemical characteristic of the solid / liquid medium contained in at least one of the drops.
3. - Procédé selon la revendication 1 ou 2, où la phase porteuse liquide a une viscosité supérieure à celle du milieu réactionnel liquide, avec un ratio de la viscosité de la phase porteuse liquide rapportée à celle du milieu réactionnel liquide des gouttes de préférence compris entre 2 et 1000. 3. - Process according to claim 1 or 2, wherein the liquid carrier phase has a viscosity greater than that of the liquid reaction medium, with a ratio of the viscosity of the liquid carrier phase relative to that of the liquid reaction medium drops preferably included between 2 and 1000.
4.- Procédé selon l'une des revendications 1 à 3, où les gouttes sont formées en continu au sein de la phase liquide porteuse, de préférence : 4. Method according to one of claims 1 to 3, wherein the drops are formed continuously within the carrier liquid phase, preferably:
- en injectant de façon séquentielle ou continue le milieu réactionnel liquide contenant les particules au sein d'un flux continu de phase liquide porteuse véhiculée au sein de l'organe d'écoulement ; ou  - By sequentially or continuously injecting the liquid reaction medium containing the particles in a continuous flow of carrier liquid phase carried within the flow member; or
- en co-injectant de façon séquentielle ou continue plusieurs flux séparés dont le mélange forme le milieu réactionnel liquide contenant les particules, au sein d'un flux continu de phase liquide porteuse véhiculée au sein de l'organe d'écoulement. by co-injecting, sequentially or continuously, several separate streams, the mixture of which forms the liquid reaction medium containing the particles, in a continuous stream of carrier liquid phase carried within the flow member.
5. - Procédé selon la revendication 4, où les gouttes sont formées en continu au sein de la phase liquide porteuse, en co-injectant de façon séquentielle ou continue : 5. - Method according to claim 4, wherein the drops are formed continuously within the carrier liquid phase, by co-injecting sequentially or continuously:
- un premier flux d'introduction comprenant au moins un réactif mis en œuvre dans la réaction chimique de l'étape (E), à l'état liquide ou solubilisé, ledit premier flux ne comprenant pas de catalyseur ; et a first feed stream comprising at least one reagent used in the chemical reaction of step (E), in the liquid or solubilized state, said first stream comprising no catalyst; and
- un deuxième flux d'introduction, distinct du premier, comprenant le catalyseur, ledit second flux étant de préférence : a second introduction stream, distinct from the first, comprising the catalyst, said second stream preferably being:
- un flux constitué du catalyseur dispersé au sein d'un milieu dispersant ; ou a stream consisting of the dispersed catalyst in a dispersing medium; or
- un flux comprend le catalyseur à l'état dispersé et un ou plusieurs réactif(s) distinct(s) du (ou des) réactif(s) présent(s) dans le premier flux d'introduction. a stream comprises the catalyst in the dispersed state and one or more reagent (s) distinct from the reagent (s) present in the first introduction stream.
6. - Procédé selon l'une des revendications 1 à 5, où les gouttes de milieu réactionnel sont formées au sein de l'organe d'écoulement au moyen d'un système d'injection débouchant au sein dudit organe d'écoulement et comprenant deux canalisations tubulaires, à savoir : 6. - Method according to one of claims 1 to 5, wherein the drops of reaction medium are formed within the flow member by means of an injection system opening into said flow member and comprising two tubular pipes, namely:
une première canalisation tubulaire, dite 'tube externe', véhiculant un premier flux comprenant au moins un réactif, liquide ou solubilisé, mis en œuvre dans la réaction de l'étape (E) ; et  a first tubular pipe, called the "outer tube", carrying a first stream comprising at least one reagent, liquid or solubilized, implemented in the reaction of step (E); and
une deuxième canalisation tubulaire, dite 'tube interne', localisée au sein de ladite première canalisation tubulaire et véhiculant un deuxième flux comprenant le catalyseur à l'état dispersé, et éventuellement un ou plusieurs réactif(s) distinct(s) du (ou des) réactif(s) présent(s) dans le premier flux d'introduction.  a second tubular pipe, called the "inner tube", located within said first tubular pipe and carrying a second stream comprising the catalyst in the dispersed state, and optionally one or more reagent (s) separate (s) of (or ) reagent (s) present in the first feed stream.
7. - Procédé selon la revendication 6, où la deuxième canalisation tubulaire, dite 'tube interne' a un diamètre interne supérieur ou égal à 5 fois, de préférence à 10 fois, et plus préférentiellement à 20 fois, la taille des objets solides formés par le catalyseur en suspension véhiculé dans le deuxième flux, ce diamètre interne du tube interne étant de préférence d'au moins 100 micromètres. 7. - The method of claim 6, wherein the second tubular pipe, called 'inner tube' has an internal diameter greater than or equal to 5 times, preferably 10 times, and more preferably 20 times, the size of solid objects formed by the suspension catalyst conveyed in the second stream, this inner diameter of the inner tube being preferably at least 100 micrometers.
8.- Procédé selon l'une des revendications 1 à 7, où la phase liquide porteuse est une huile fluorée, la paroi interne de l'organe d'écoulement comprenant de préférence, au moins en surface, un matériau organique fluoré. 8. A process according to one of claims 1 to 7, wherein the carrier liquid phase is a fluorinated oil, the inner wall of the flow member preferably comprising, at least on the surface, a fluorinated organic material.
PCT/EP2012/061926 2011-07-06 2012-06-21 Solid/liquid heterogeneous catalysis in a millifluidic or microfluidic medium WO2013004509A1 (en)

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020508854A (en) * 2017-02-23 2020-03-26 ワッカー ケミー アクチエンゲゼルシャフトＷａｃｋｅｒ Ｃｈｅｍｉｅ ＡＧ Method and apparatus for hydrolysis of compounds

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008043860A1 (en) * 2006-10-13 2008-04-17 Rhodia Operations Process for preparing a polymer
FR2907030A1 (en) 2006-10-13 2008-04-18 Rhodia Recherches & Tech Managing plugs in fluid stream, e.g. in millifluid analysis system, includes forming plugs in carrier phase in situ from two immiscible fluids flowing in upstream tubes
FR2928209A1 (en) * 2008-03-03 2009-09-04 Rhodia Operations Sas METHOD AND PLANT FOR DETERMINING AT LEAST ONE PARAMETER OF A PHYSICAL AND / OR CHEMICAL PROCESSING

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2008043860A1 (en) * 2006-10-13 2008-04-17 Rhodia Operations Process for preparing a polymer
FR2907030A1 (en) 2006-10-13 2008-04-18 Rhodia Recherches & Tech Managing plugs in fluid stream, e.g. in millifluid analysis system, includes forming plugs in carrier phase in situ from two immiscible fluids flowing in upstream tubes
FR2928209A1 (en) * 2008-03-03 2009-09-04 Rhodia Operations Sas METHOD AND PLANT FOR DETERMINING AT LEAST ONE PARAMETER OF A PHYSICAL AND / OR CHEMICAL PROCESSING

Non-Patent Citations (7)

* Cited by examiner, † Cited by third party
Title
A. UFER ET AL: "Liquid/Liquid Slug Flow Capillary Microreactor", CHEMICAL ENGINEERING & TECHNOLOGY, vol. 34, no. 3, 5 January 2011 (2011-01-05), pages 353 - 360, XP055020495, ISSN: 0930-7516, DOI: 10.1002/ceat.201000334 *
A. UFER ET AL: "Suspension catalysis in a liquid-liquid capillary microreactor", CHEMICAL ENGINEERING JOURNAL, vol. 167, no. 2-3, 23 October 2010 (2010-10-23), pages 468 - 474, XP055020497, ISSN: 1385-8947, DOI: 10.1016/j.cej.2010.09.088 *
ADVANCED SYNTHESIS AND CATALYSIS, vol. 351, 2009, pages 3260 - 3268
ASHLEIGH B. THEBERGE ET AL: "Suzuki-Miyaura coupling reactions in aqueous microdroplets with catalytically active fluorous interfaces", CHEMICAL COMMUNICATIONS, no. 41, 28 August 2009 (2009-08-28), pages 6225, XP055020503, ISSN: 1359-7345, DOI: 10.1039/b911594c *
CHRISTOPHER HARDACRE ET AL: "Friedel-Crafts Benzoylation of Anisole in Ionic Liquids: Catalysis, Separation, and Recycle Studies", ORGANIC PROCESS RESEARCH & DEVELOPMENT, vol. 12, no. 6, 21 November 2008 (2008-11-21), pages 1156 - 1163, XP055020501, ISSN: 1083-6160, DOI: 10.1021/op800134k *
JOURNAL OF AMERICAN CHEMICAL SOCIETY, vol. 124, 2002, pages 13360 - 13361
NICOLAS LORBER ET AL: "Investigating Acrylic Acid Polymerization by Using a Droplet-Based Millifluidics Approach", MACROMOLECULAR SYMPOSIA, vol. 296, no. 1, 1 October 2010 (2010-10-01), pages 203 - 209, XP055020499, ISSN: 1022-1360, DOI: 10.1002/masy.201051030 *

Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2020508854A (en) * 2017-02-23 2020-03-26 ワッカー ケミー アクチエンゲゼルシャフトＷａｃｋｅｒ Ｃｈｅｍｉｅ ＡＧ Method and apparatus for hydrolysis of compounds

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