Device for producing organometallic compounds

Abstract

The present invention relates to a device for producing organometallic compounds, comprising: a reactor (1) having, at a first end (1a), an inlet (12) for continuously feeding the reactor (1) with reagent; a sedimentation means (2) connected to the reactor (1) at the end opposite the first end (1a) of the reactor (1), and accommodating a supply means (3); as well as a recirculation loop (4), and an outlet (5) for a fluid.

Description

[0001] DEVICE FOR PRODUCING ORGANOMETALLIC COMPOUNDS

[0002] The present invention relates to a device for producing organometallic compounds, to a method for producing said compounds and also to a method implemented in the proposed device.

[0003] The present invention relates to the field of organometallic chemistry, which encompasses compounds containing bonds between carbon atoms and metal atoms, including metal alkyls / aryls, metal carbides (e.g., WC), metal alkylidenes and arylidenes (with CC double bond), metallocenes (ferrocenes), metal-carbon transition complexes, etc.

[0004] There are different types of devices for forming organometallic compounds.

[0005] The general principle is to react metal with a reagent in the presence of a solvent. The reaction typically takes place in a reactor.

[0006] For example, the production of butyllithium (BuLi) can be carried out in a glass or stainless steel reactor equipped with a gas outlet and a cooling system since the reaction is exothermic. Often, it is necessary to use a mechanical stirrer to ensure constant agitation so that the reaction can proceed smoothly and efficiently within the reactor. A thermostatic bath to control and maintain the reaction temperature can also be used to manage the temperature within the reactor.

[0007] WO 02 / 20151 illustrates the production of BuLi using a series reactor system. The solvent (hexane) and the reactant (BuCl) are introduced into the upper part of the reactor, followed by lithium addition in the form of chips. The organometallic compound, in this case BuLi, is recovered from the lower part of the reactor, along with unreacted BuCl and the solvent. This is then introduced into a second reactor (similar to the first reactor) to produce BuLi at a satisfactory yield.

[0008] Unfortunately, this type of system requires a coolant surrounding the reactor, which does not allow for good management of the overall thermal efficiency during the reaction process. These reactors do not allow for a continuous process and are not economically viable on an industrial scale. Finally, a series of purification methods must be implemented, which complicates the on-board process.

[0009] Document CN 212595730 relates to a reactor designed to provide a Grignard reagent in the presence of a heat exchanger. The solvent is injected from the bottom of the reactor and has a complex system for introducing the mixture comprising the solvent and the substrate into the reactor. The product of interest is recovered, filtered and then collected in the middle of the reactor. Unfortunately, a significant quantity of solid particles accompanies the product of interest at the outlet of the reactor.

[0010] There is therefore a real need to provide a device that allows industrial-scale production that is economically viable, while ensuring a continuous process with optimization in the production of the compound of interest in terms of yield, material exchange, the number of subsequent purification steps of the compound of interest, ease of installation on site, reaction control and durability of the system over time.

[0011] To solve these problems, the present invention provides a device for producing organometallic compounds comprising: - A reactor arranged to contain a substrate containing a metal and forming a bed of solid particles, said reactor comprising, at a first end located downstream thereof, an inlet for continuously supplying said reactor with reagent, and optionally a solvent,

[0012] - A sedimentation means being connected to said reactor, opposite said first end of said reactor, and receiving a supply means arranged to deliver said substrate above the bed of solid particles,

[0013] - A recirculation loop which comprises an extraction means located upstream of said device, an injection means downstream of said reactor (preferably being adjacent to said inlet of said reactor), and a thermal regulation means, preferably a heat exchanger, said recirculation loop being arranged to continuously extract a fluid which comprises (at the outlet of the device) a part of said reagent and an organometallic compound (in the majority quantity in the fluid), to cool or heat said fluid and continuously inject it into said reactor by said injection means,

[0014] - An outlet for said fluid.

[0015] In operation, the reactor includes an inlet (at the bottom) through which a reactant can be introduced which will make its way into the bed of solid particles with which it will react to form the organometallic compound which will be able to reach the outlet of the device. The device allows a homogeneous reaction within the bed of solid particles without necessarily promoting individual paths through it. Thus, the production efficiency of the fluid is favorable and advantageous for the user.

[0016] Thermal management is achieved through the recirculation loop, which also helps generate sufficient turbulence in the bed of solid particles to allow the reaction to proceed homogeneously within the reactor. This allows the reactant to be consumed efficiently through adequate mass exchange.

[0017] The presence of the supply means makes it possible to supply the substrate above the bed of solid particles without disturbing the fluid that is generated during the process. Thus, the substrate is supplied in the opposite direction to the upward movement of the fluid. The supply means preferentially reduces the upward velocity of the fluid towards the outlet, compared to the upward velocity of the fluid within the reactor.

[0018] The device according to the invention, in operation, makes it possible on the one hand to provide a substrate which will be able to sediment at the bottom of the reactor and, on the other hand, to feed it with reagent starting from the lower part of the reactor towards the upper part of the reactor (counter to the flow direction of the substrate). Thus, when the bed of solid particles is formed, the substrate is gradually consumed following the reaction with the reagent. Then, substrate can be added over time when necessary (read, semi-continuously or continuously) in order to keep a bed of solid particles ready to react with the reagent.

[0019] The device according to the invention offers a high conversion rate, preferably greater than 70%, more preferably greater than 99%, more preferably greater than 99.8%. Thus, the compound of interest can more easily be collected at the end of the process, while being substantially free of residual reagent, preferably the residual reagent is present in the fluid in an amount of less than 30%, more preferably less than 1%, more preferably still less than 0.2%). It is therefore not necessary to carry out complex filtration steps within or downstream of the reactor. A single reactor is sufficient to carry out the reaction, which is particularly advantageous, and in combination with the recirculation loop, the device allows sustainable and continuous management over time, without deteriorating its reaction performance.

[0020] Thanks to the device according to the invention, the fluid which comprises the reagent and (mainly at the outlet of the device) the organometallic compound, and possibly in the presence of a solvent, can reach the outlet of the device without being polluted by unreacted substrate.

[0021] Preferably, said sedimentation means comprises an inclined internal wall which forms an angle y, with an internal face of said reactor, of a value greater than 180°, said inclined internal wall relative to said internal face of said reactor being arranged to allow an upward passage of said fluid towards said outlet of said device.

[0022] Preferably, said inclined internal wall (6) of the sedimentation means (2) has a first end (6a) and a second end (6b). The first end (6a) of the inclined wall (6) is adjacent (or connected) to the second end (1b) of the internal face (7) of said reactor (1).

[0023] Advantageously, said second end (6b) of said inclined internal wall (6) of the sedimentation means (2) is adjacent (or connected) to the outlet (5) of said device.

[0024] Even more advantageously, said inclined inner wall (6) of the sedimentation means (2) is a segment which extends from the first end (6a) of said wall (6) to the second end (6b) of said inclined inner wall (6). Said segment may be partly curved and / or partly straight or a combination of both. Preferably, said segment is (mostly) straight. Preferably, said inclined inner wall (6) of the sedimentation means (2) is (mostly) straight.

[0025] Preferably, said supply means (3) has a proximal end (3a), at which there is an opening which has a section X and in that the reactor has a section Y which is greater than or equal to said section X. This makes it possible to further reduce the upward speed of the fluid which heads towards the outlet of said device. Also, this makes it possible to provide a regular supply of substrate without the upward flow of fluid carrying substrate particles towards the outlet of the device.

[0026] Particularly advantageously, the proximal end of said supply means, which is adjacent to said inclined wall of said sedimentation means (2), is located inside said sedimentation means (2).

[0027] Even more advantageously, the distal end of the supply means is located outside said sedimentation means (2).

[0028] Preferably, said opening located at (at) the proximal end of said supply means is oriented towards said second end of said reactor.

[0029] According to an advantageous embodiment, said sedimentation means comprises a rise velocity homogenization element arranged to optimize the passage of the fluid towards the outlet (5) of the device. In addition, this element makes it possible to limit the presence of the substrate in the upper part of the sedimentation means (2). The rise velocity homogenization makes it possible to limit the maximum rise velocity through preferential paths within the sedimentation means (2), which greatly limits the risk of substrate particles being entrained by the fluid towards the outlet of the device. The rise velocity homogenization element (8) is also arranged to distribute the ascending fluid flows homogeneously in the sedimentation element and arranged to serve as a filter.

[0030] Also, said homogenizing element makes it possible to retain a quantity of substrate in order to reduce as much as possible its presence in said fluid when the latter reaches the outlet of said device. This makes it possible to limit the presence of said substrate in said fluid. The fluid will pass through the homogenizing element to reach the outlet of the device.

[0031] According to a preferred embodiment, said ascending speed homogenization element comprises a perforated plate which extends on either side of said supply means or which extends transversely, relative to said supply means, within said sedimentation means (2).

[0032] Advantageously, said outlet of said device is located at said sedimentation means (2), preferably in the upper part thereof, more preferably at the upper edge of said sedimentation means (2). This embodiment is particularly interesting in that the fluid is directed into the sedimentation means (2) in the direction of the upper part of the sedimentation means (2) towards the outlet of the device. This makes it possible to reduce the quantity of substrate in the fluid which is collected at the outlet.

[0033] Particularly advantageously, the combination between the sedimentation means and the supply means allows an effective and progressive reduction of the upward speed of the fluid in said sedimentation means, when the device is in operation. According to a particular embodiment, a filter for the substrate is positioned at the outlet of said device, preferably at the level of the upper part of said sedimentation means (outside of said device), so as to prevent the passage of particles having a size greater than or equal to 250 μm, preferably greater than or equal to 50 μm, more preferably greater than or equal to 10 μm.

[0034] Preferably, said outlet of said device is located in the upper part of the sedimentation means (2) or at the level of said second end of said inclined internal wall of said sedimentation means (2).

[0035] According to an advantageous embodiment, said extraction means (4a) of said recirculation loop (4) is located at the level of said sedimentation means (2), preferably at the same level as said outlet (5) of said device, or at the high level of said reactor (1).

[0036] According to a particular embodiment, said extraction means of said recirculation loop is located at the same location as the outlet of said device. Thus, part of the fluid is recovered at the outlet and another part can be extracted and reinjected into the reactor by means of the recirculation loop. In concrete terms, a single outlet conduit is provided and then the conduit is split in order to define an outlet path and an extraction path from the recirculation loop.

[0037] Even more advantageously, said reactor and said sedimentation means are arranged to be (completely) filled with said fluid, possibly in the presence of a solvent, when the device operates continuously. This does not exclude the presence of the substrate forming the bed of solid particles within the reactor (present in a smaller quantity expressed in volume compared to that of the fluid / reagent). Thus, said fluid, possibly in the presence of a solvent, completely covers the bed of solid particles, when the device operates continuously.

[0038] According to a particularly preferred embodiment of the invention, the device has a feed lock which contains a free space for said substrate (before introduction into the reactor), said lock being located above said sedimentation means (2) and being arranged to deliver the substrate into said supply means.

[0039] Said supply airlock being operable by means of a system comprising a series of valves.

[0040] Said free space being arranged to be filled with an inert gas, preferably nitrogen, argon or any other equivalent.

[0041] Preferably, said recirculation loop comprises a filtration means.

[0042] Preferably, the recirculation loop includes a recirculation pump.

[0043] According to a preferred embodiment, the proximal end of said supply means is located on the side of the second end of said reactor.

[0044] Preferably, the proximal end (3a) of said supply means (3) is adjacent to said inclined internal wall (6) of said sedimentation means (2) and is separated therefrom by a distance (d) sufficient to allow a reduction in the upward velocity of said fluid as it passes through said sedimentation means towards said outlet (5) of said device.

[0045] Advantageously, the shortest distance between the proximal end of said supply means and the inclined wall of the sedimentation means (2) defines a section dx which extends all around the internal wall of said sedimentation means and which defines a total surface area (for example as illustrated in Figure 2 in hatching). Thus, a passage area for the fluid is available within the sedimentation means at the level of the section dx. The section dx allows a reduction in the upward speed of said fluid during its passage in said sedimentation means towards said outlet of said device.

[0046] According to an advantageous embodiment, the section dx is between the internal wall of the sedimentation means and the proximal end of the supply means.

[0047] Preferably, the sedimentation means has at least two sections (dx and dx'). In this case, the section (dx) and the section (dx') do not have the same value. The section (dx') is symmetrically opposite to the section (dx) and also corresponds to a certain distance between the proximal end of said supply means and the inclined wall of the sedimentation means. The total surface area defined by the sections (dx and dx') being the sum of the section dx and the section dx' along the internal wall of the sedimentation means (2).

[0048] Preferably, the ratio between the total surface area defined by the section dx or the sum of the sections dx and dx', and the section Y of the reactor is preferably greater than or equal to 1, in order to further optimize the sedimentation of the substrate within the device.

[0049] Advantageously, the section dx or the sum of the sections dx and dx' is greater than or equal to the section Y of the reactor so as to reduce the upward velocity of the fluid in the sedimentation means (2) compared to the upward velocity of the fluid in the reactor. Preferably, the following elements are expressed according to the formulations described below:

[0050] The dx section > the Y section, , , .

[0051] The section

[0052] The section dx = A2- Ai , diameter of the supply medium r1 1 = - 2, diameter of the supply means h l ~ 2 tan(270 - y)

[0053] The value dx can optionally correspond to the sum of dx and dx'.

[0054] According to an advantageous embodiment, the section upstream of the reactor can define the section of the reactor (without being limited by its geometry).

[0055] Advantageously, the section of the proximal end of the supply means may define the section of the supply means (without being limited by its geometry). Preferably, the diameter of the reactor is cylindrical and has a constant diameter over its entire height.

[0056] According to a preferred embodiment, the supply means is in the form of a longitudinal element, preferably in the form of a cylinder, cone or tube.

[0057] Other characteristics and advantages of the device according to the invention will emerge from the description provided below and from the corresponding claims.

[0058] The present invention also relates to a process for producing an organometallic compound comprising the following steps:

[0059] - Adding a substrate containing a metal upstream of a reactor which is connected to a sedimentation means which accommodates a means of supplying said substrate, until a bed of solid particles is formed within said reactor,

[0060] - Continuously supplying said reactor with reagent, optionally with a solvent, in the opposite direction of flow of said substrate, until a fluid is formed which comprises a part of said reagent and the organometallic compound,

[0061] - Setting up a recirculation loop: continuous extraction of said fluid and / or said reagent, cooling or heating thereof and continuous injection of said fluid and / or said reagent, in the opposite direction of flow of said substrate,

[0062] - Recovery, at the outlet of said device, of said fluid, characterized in that, during the process, said substrate is fed, in the opposite direction to the upward movement of the fluid formed, into said supply means, which is partially housed in said sedimentation means, in order to deliver said substrate above the bed of solid particles initially formed, and in that said supply means allows a reduction in the upward speed of said fluid formed during the reaction, during its passage through said sedimentation means, preferably towards the outlet of said device.

[0063] Preferably, said substrate has a sedimentation velocity in said reactor which is greater than the rise velocity of said fluid in said reactor.

[0064] More preferably, said upward speed of said fluid in the sedimentation means is gradually reduced until reaching the outlet of the device.

[0065] Advantageously, the rate of rise of said fluid, when it is in said sedimentation means, is at least 1 time, at least 1.5 times, preferably 3 times, more preferably at least 5 times lower than the rate of rise of said fluid in said reactor. Even more preferably, the rate of rise of said fluid, when it is in said sedimentation means, can be up to 10 times, advantageously up to 20 times lower than the rate of rise of said fluid in said reactor.

[0066] More advantageously, the upward velocity of said fluid in said sedimentation means is preferably less than 2 mm / s, more preferably less than 1.5 mm / s, even more preferably less than 1 mm / s.

[0067] More advantageously, the ratio between the volume flow rate of said fluid in the recirculation loop and the volume flow rate of said reagent (optionally in the presence of said solvent) added to the reactor is between 1:1 and 500:1, preferably between 1:1 and 70:1.

[0068] Even more advantageously, the reactor is completely filled with reactant and / or fluid. Also, the reactor comprises the bed of solid particles. Preferably, the substrate has been added into the reactor until more than half (preferably %) of its volume is formed of the bed of solid particles, thus leaving a part (by volume) of said reactor filled with said reactant and / or said fluid, above said bed.

[0069] Preferably, said substrate is added (semi-continuously or continuously) above said previously formed bed of solid particles, preferably in the liquid present above said bed, during the reaction process at controlled time frequencies.

[0070] More preferably, when the device is in operation, the reactor and the sedimentation means (2) are completely filled with reagent and / or fluid, possibly in the presence of solvent. Thus, when the device operates continuously, the reactor and the sedimentation means (2) comprise (mostly) liquid which can be chosen from fluid, reagent, solvent and their combinations. Also, it is obvious that the bed of solid particles is present in the reactor. Thus, the liquid can completely fill the volume provided by the reactor and the sedimentation means (2), while maintaining the bed of solid particles in the reactor.

[0071] Preferably, it is also possible for the liquid (reagent and / or fluid and / or solvent) to mainly fill the volume supplied by the supply means, while possibly leaving a free space (for an inert gas) above the reagent / fluid present in the supply means.

[0072] More preferably still, said reagent, and optionally the solvent, has an average residence time in said device of at least 0.1 hour (h).

[0073] Thus, if the volume of the reactor is for example less than 10 liters, a residence time of between 0.7 and 2.4 h will be preferred within the reactor, preferably at a flow rate of between 1 and 20 l / h, more preferably between 1 and 15 l / h.

[0074] Other characteristics and advantages of the method according to the invention will emerge from the description provided below and from the corresponding claims.

[0075] The present invention also relates to a method for producing an organometallic compound which is implemented in the device according to the invention. The method comprises the following steps:

[0076] Add a substrate containing a metal upstream of said reactor until a bed of solid particles forms within said reactor,

[0077] Continuously supplying said reactor with reagent, optionally with a solvent, in the opposite direction of flow of said substrate, until a fluid is formed which comprises a portion of said reagent and the organometallic compound,

[0078] Setting up a recirculation loop: continuous extraction of said fluid and / or said reagent, cooling or heating thereof and continuous injection of said reagent and / or fluid, in the opposite direction of flow of said substrate, Recovery, at the outlet of said device, of said fluid, characterized in that, during the process, said substrate is supplied, in the opposite direction to the upward movement of the fluid formed in said supply means, which is partially housed in said sedimentation means, in order to deliver said substrate above the bed of solid particles initially formed, and in that said supply means allows a reduction in the upward speed of said fluid formed during the reaction during its passage through said sedimentation means, preferably towards the outlet of said device.All the characteristics listed above for the device and for the method can be combined with the method implemented in the device according to the invention. These are thus repeated below.

[0079] Preferably, said substrate has a sedimentation velocity in said reactor which is greater than the rise velocity of said fluid in said reactor.

[0080] More preferably, said upward speed of said fluid in the sedimentation means (2) is gradually reduced until reaching the outlet of the device.

[0081] Advantageously, the rate of rise of said fluid, when it is in said sedimentation means, is at least 1 time, at least 1.5 times, preferably 3 times, more preferably at least 5 times lower than the rate of rise of said fluid in said reactor. Even more preferably, the rate of rise of said fluid, when it is in said sedimentation means, can be up to 10 times, advantageously up to 20 times lower than the rate of rise of said fluid in said reactor.

[0082] More advantageously, the upward velocity of said fluid in said sedimentation means is preferably less than 2 mm / s, more preferably less than 1.5 mm / s, even more preferably less than 1 mm / s.

[0083] More advantageously, the ratio between the volume flow rate of said fluid in the recirculation loop and the volume flow rate of said reagent (optionally in the presence of said solvent) added to the reactor is between 1:1 and 500:1, preferably between 1:1 and 70:1.

[0084] Even more advantageously, the reactor is completely filled with reactant and / or fluid. Also, the reactor comprises the bed of solid particles. Preferably, the substrate has been added into the reactor until more than half (preferably %) of its volume is formed of the bed of solid particles, thus leaving a part (by volume) of said reactor filled with said reactant and / or said fluid, above said bed.

[0085] Preferably, said substrate is added (semi-continuously or continuously) above said previously formed bed of solid particles, preferably in the liquid present above said bed, during the reaction process at controlled time frequencies.

[0086] More preferably, when the device is in operation, the reactor and the sedimentation means (2) are completely filled with reagent and / or fluid, possibly in the presence of solvent. Thus, when the device operates continuously, the reactor and the sedimentation means (2) comprise (mostly) liquid which can be chosen from fluid, reagent, solvent and their combinations. Also, it is obvious that the bed of solid particles is present in the reactor. Thus, the liquid can completely fill the volume provided by the reactor and the sedimentation means (2), while maintaining the bed of solid particles in the reactor.

[0087] Preferably, it is also possible for the liquid (reagent and / or fluid and / or solvent) to mainly fill the volume supplied by the supply means, while possibly leaving a free space (for an inert gas) above the reagent / fluid present in the supply means.

[0088] More preferably still, said reagent, and optionally the solvent, has an average residence time in said device of at least 0.1 hour (h).

[0089] Thus, if the volume of the reactor is for example less than 10 liters, a residence time of between 0.7 and 2.4 hours will be preferred within the reactor, preferably at a flow rate of between 1 and 20 l / h, more preferably between 1 and 15 l / h.

[0090] The invention is illustrated below based on an embodiment illustrated in Figure 1. Several other features are also provided in order to define the invention in more detail.

[0091] The expression "within the reactor" must be understood to mean that the element in question is located inside the reactor.

[0092] The average residence time is determined according to the following formula: total volume liquid phase total volume flow rate of the fluid outlet

[0093] Where, the total volume of the liquid phase corresponds to the volume of the reagent, fluid and solvent contained in the reactor, the sedimentation means (2), the supply means and the recirculation loop.

[0094] The term "substrate is fed semi-continuously" means that it is added in quantity at controlled frequencies to feed the reactor with substrate. This allows a near-constant bed of solid particles to be maintained throughout the process so that the reaction can be carried out by continuously feeding the reactor from bottom to top with reactant, possibly with a solvent.

[0095] Preferably, the substrate is fed continuously within the device or semi-continuously as defined above.

[0096] The rate of ascent (m / s) at a given location is determined by the ratio between the volume flow rate (m 3 / s) at a given location of the device and the surface area of ​​said section (m 2). The term "substrate" means a substrate containing a metal and may be selected from the group consisting of solid particles of a metal, salts containing a metal, solid compositions based on a metal, and mixtures thereof.

[0097] The device according to the invention comprises a reactor which is arranged to contain a bed of solid particles, preferably non-fluidized. This means that the non-fluidized bed of solid particles corresponds to a device in which the substrate is contained in the reactor without exhibiting fluidization behavior. In other words, a non-fluidized bed of solid particles is characterized by the fact that the substrate remains in place, without being in suspension, and generally occupies a relatively fixed or slowly moving position inside the reactor, unlike a fluidized bed in which the solid particles move and circulate freely according to turbulent movements.

[0098] Thus, the device according to the invention which is arranged to contain a non-fluidized bed of solid particles allows sufficient contact between the solid substrate and the reagent to form the organometallic compound.

[0099] Preferably, the bed of solid particles is non-fluidized or fluidized.

[0100] Preferably, the recirculation loop allows a certain degree of turbulence to be established within the reactor, which promotes the reaction process.

[0101] In the context of the invention, the expression "upstream of the reactor" means "in the upper part of the reactor". Similarly, the expression "downstream of the reactor" means in the lower part of the reactor. In addition, the notion of upstream and the notion of downstream are defined in relation to the flow direction of the substrate within the reactor. Thus, as the substrate is delivered from the top of the reactor to the bottom of the reactor, upstream of the reactor designates an upper part of the reactor (where the substrate is introduced) and downstream designates a lower part of the reactor (bottom of the reactor). Thus, the flow direction of the substrate defines upstream and downstream of the reactor.

[0102] The term "fluid" implies that it includes the unreacted reagent and the organometallic compound.

[0103] When the term "reagent" is used in the present invention, it means any liquid or gaseous reagent that can produce an organometallic compound with or in the absence of a solvent. Thus, the term "reagent" may at any time be replaced by "reagent with a solvent".

[0104] The term "section" refers to a dimension of a cross-sectional plane and can thus designate a surface, possibly a diameter of an object under consideration. The term diameter is preferred if the shape of the object under consideration is spherical, circular or conical.

[0105] Thus, the reagent can be introduced from the bottom of the reactor (downstream of the reactor) to the top of the reactor (upstream of the reactor) and thus, in the opposite direction to the flow direction of the substrate.

[0106] In organometallic compounds, the metal may be bonded directly to one or more carbon atoms, forming a metal-carbon bond. These bonds may be single, double, or triple. Commonly encountered metals in organometallic compounds include metals selected from the group consisting of alkali metals, alkali metals, lanthanides, actinides, transition metals, post-transition metals (poor metals), metalloids, and mixtures thereof. Orgonometollilic compounds have numerous applications in various fields, such as catalysis, organic synthesis, electrochemistry, and materials chemistry. They can also serve as precursors in the manufacture of catalysts, reagents, and metal complexes used in a wide range of chemical reactions. Organometallic compounds can thus be used as intermediates in other reaction processes.

[0107] The organometallic compounds can be selected from metal alkyls / aryls, metal carbides (e.g., WC), metal alkylidenes and arylidenes (with CC double bond), metallocenes (ferrocenes), metal-carbon transition complexes, etc.

[0108] Metal alkyls are organometallic compounds in which a metal atom is bonded to an alkyl group, such as methyl (CH3), ethyl (C2H5), propyl (C3H7), etc.

[0109] Metal aryls are organometallic compounds in which a metal atom is bonded to an aryl group, which is a group derived from an aromatic compound such as benzene.

[0110] Metal carbides are organometallic compounds in which a metal atom is bonded to one or more carbon atoms in a carbide-like structure. A well-known example is tungsten carbide (WC).

[0111] Metal alkylidenes and arylidenes are organometallic compounds containing alkylidene or arylidene ligands, which are functional groups with a carbon-carbon double bond. They can be bonded to a metal atom. Metallocene compounds are organometallic compounds comprising metallocene-type rings, in which one or more metal atoms are sandwiched between two aromatic hydrocarbon rings, such as ferrocene.

[0112] Metal-carbon transition complexes are organometallic compounds in which a metal atom is bonded to a carbon ligand such as an alkene, alkyne, or carbene. These complexes are often used in catalysis and organic synthesis.

[0113] In a non-limiting manner, the organometallic compounds may for example be metal alkyls (RM), metal aryls (Ar-M), metal carbides (MC), metal alkylidenes (R=C(R)-M), metal arylidenes (Ar=C(=CR2)-M), metallocene compounds ((Cyclopentadienyl)M), metal allylic compounds (R2C=CH-CH2-M), metal carbenoids (2C:M), metal acyl compounds (RCO-M), metal alkenyl compounds (R2C=CR'-M), metal carbenes (R2C:M), metal carbynes (RC=M), metal vinyl compounds (2C=CR'-M), metal alkynyl compounds (RC=CM), metal benzene compounds (Ar-M), metal heterocyclic compounds (RM), polynuclear metal compounds ((Ligand)M n ), metal cluster compounds ((Ligand)Mn), chiral metal compounds: RM (R = chiral group, M = metal), metal compounds with multiple metal-carbon bonds

[0114] (M=C=M).

[0115] Preferably, the fluid leaving the device according to the invention mainly comprises a solvent where appropriate, and the organometallic compound.

[0116] The reactor according to the invention may have a longitudinal shape and is designed to contain the bed of solid particles. In the lower part, at a first end of the reactor, there is an inlet for continuously supplying said reactor with reagent (possibly with a solvent). The inlet may be connected to a supply conduit for said reagent, and possibly the solvent.

[0117] The reagent may be selected from the group comprising halide reagents (preferably methyl bromide, methyl chloride, methyl iodide, ethyl bromide, ethyl chloride, ethyl iodide, phenyl bromide, phenyl chloride, phenyl iodide), alkyl compounds, aryl compounds, alkyne compounds (e.g. ethyne (acetylene), an alkyne which may be used for the synthesis of organometallic complexes), precursor organometallic compounds (such as triphenyltin chloride), lithium or sodium-based reagents (organolithium reagents, such as butyllithium and methyllithium).

[0118] The solvent may be selected from the group comprising saturated hydrocarbons, aromatic hydrocarbons, ethers, polyethers, tertiary amines, other aprotic solvents and mixtures thereof.

[0119] Preferably, the solvent may be a solvent other than water selected from the group comprising ether, preferably cyclopentyl methyl ether, tetrahydrofuran, dioxane, dimethoxyethane, diethyl ether, 2-methyl-tetrahydrofuran, 4-methyltetrahydropyran, methyl-tert-butyl ether, and mixtures thereof.

[0120] The solvent other than water can be combined with other aprotic organic solvents, especially toluene.

[0121] Advantageously, the solvent according to the invention is substantially free of water, that is to say it contains less than 1% by weight of water, preferably less than 0.5% by weight of water, more preferably less than 0.25% of water, even more preferably less than 0.1% of water. Even more advantageously, the solvent comprises less than 0.01% by weight of water. These values ​​are expressed relative to the total weight of the solvent.

[0122] Preferably, the solvent is predominant in mass quantity relative to the organometallic compound formed during the process or vice versa, within the reactor and at the outlet of the device. In the absence of solvent, the organometallic compound is predominant in quantity at the outlet of the device.

[0123] The metal-containing substrate is any metal-containing compound capable of giving rise to the formation of an organometallic compound wherein the metal may advantageously be selected from the group comprising a metal, preferably magnesium, zinc or lithium. Advantageously, the metal is an alkali metal, a lino-earth metal, preferably magnesium, a poor metal, preferably aluminum, a transition metal, preferably zinc or any other metal capable of leading to the formation of an organometallic compound.

[0124] The reactor has a second end, located opposite its first end, and which is connected to the sedimentation means (2) which accommodates the supply means which makes it possible to deliver the substrate containing a metal into the reactor continuously or semi-continuously.

[0125] When it is indicated that the sedimentation means (2) accommodates the supply means, this means that a part of the supply means is contained in the sedimentation means (2) and that another part is outside the sedimentation means (2). Preferably, the supply means has a first proximal end located inside the sedimentation means (and oriented towards the second end of the reactor) and a distal end, opposite said proximal end, located outside the sedimentation means. This makes it possible to facilitate the supply of substrate to the reactor. Also, this makes it possible to benefit from a free zone (above ref. 10a) above the reagent / fluid to contain an inert gas and allow easy sedimentation of the substrate during the process.

[0126] More preferably, the majority of the sedimentation medium is located outside the sedimentation medium.

[0127] The sedimentation means advantageously has a first narrow open end and a second closed end that is wider (compared to the first end). More specifically, the first end has a section A that is smaller than the section B of the second closed end of said sedimentation means. The first open end is oriented facing the second end of the reactor, preferably rests (is aligned) on the periphery of the reactor at this second end. This connection between the sedimentation means and the reactor is watertight.

[0128] Advantageously, the sedimentation means comprises at said second end an open part for receiving the supply means, preferably in its center. The connection between the two being watertight.

[0129] Thus, the substrate can be introduced into the airlock in such a way as to comply with the operational conditions of the device (P and T). Part of the airlock has a free space supplied with gas in order to be able to maintain the reactor and the sedimentation means at the desired pressure and in the reaction conditions necessary for the proper conduct of the process. The feed airlock also makes it possible to feed the device with substrate in such a way as to allow efficient sedimentation, without disturbing the device according to the invention.

[0130] It should be noted that advantageously, the reagent is not present in the free space of the feed airlock. Furthermore, no liquid (reagent, solvent, fluid, etc.) is present in this free space located above the sedimentation means.

[0131] It will therefore be preferred to have the sedimentation means and the reactor filled with the reagent, while having the reactor filled with the substrate according to the planned conditions. Indeed, it is possible to create a space (Z), above the bed of solid particles (9), filled with liquid in the reactor when it is not completely filled with substrate containing a metal. In this case, the substrate will have completely sedimented at the bottom of the reactor leaving a space for the reagent / fluid during the operating process. Preferably, this space is mainly filled with fluid.

[0132] Preferably, the reagent / fluid reaches the % of the level of the supply means (3) in height, as illustrated in Figure 1.

[0133] Advantageously, the proximal end (3a) of the supply means is located at a sufficient distance (13) from the homogenization element (8) or the outlet 5 of the device or the extraction means (4a) or at the upper edge of the sedimentation means (2), which are located in the upper part of the sedimentation means. This makes it possible to deliver the substrate above the bed of solid particles while limiting the movement of a part of the substrate in the upper part of the sedimentation means. This is particularly useful for the user. The following references are used in the context of the present invention, with reference to Figure 1, without being limited thereto:

[0134] The reactor (1)

[0135] The first end (la) of the reactor (1)

[0136] The second end (1 b) of the reactor (1)

[0137] The symmetrically opposite end (1 b') to the second end (1 b) of the reactor

[0138] The means of sedimentation (2)

[0139] The means of supply (3)

[0140] The proximal end (3a) of the supply means (3)

[0141] The distal end (3b) of the supply means (3)

[0142] The recirculation loop (4)

[0143] The extraction means (4a) of the recirculation loop (4)

[0144] The injection means (4b) of the recirculation loop (4)

[0145] The thermal regulation means (4c) of the recirculation loop (4)

[0146] The output of the device (5)

[0147] The inclined wall (6) of the sedimentation means (2)

[0148] The first end (6a) of the inclined wall (6) of the sedimentation means (2)

[0149] The second end (6b) of the inclined wall (6) of the sedimentation means (2)

[0150] The internal face (7) of the reactor (1)

[0151] The ascending speed homogenizing element (8) The bed of solid particles (9)

[0152] Minimum level (10b) of fluid / reagent in the supply means (3)

[0153] Maximum level (10a) of fluid / reagent in the supply means (3)

[0154] Difference between the minimum level (10b) and the maximum level (10a) of fluid / reagent in the supply means (3)

[0155] A series of valves (1 1 )

[0156] Reactor inlet (12)

[0157] Distance (13) located between the proximal end (3a) and the homogenizing element (8) or the outlet (5) of the device or the extraction means (4a) or at the upper edge of the sedimentation means (2)

[0158] The angle y defined between the inclined wall (6) of the sedimentation means (2) and the internal face (7) of the reactor (1), of a value greater than 180°

[0159] The space (Z) located between the second end (1 b) of the reactor and the surface of the bed of solid particles (9).

[0160] Section X located at the proximal end (3a) of the supply means (3)

[0161] The Y section of the reactor

[0162] The shortest distance (d) between a part of the proximal end (3a) of the supply means (3) and the inclined wall (6) of the sedimentation means (2)

[0163] The shortest distance (d') between a part of the proximal end (3a) of the supply means (3) and the other inclined wall (6') of the sedimentation means (2), that which is symmetrically opposite the inclined wall (6) of the sedimentation means.

[0164] In the context of the present invention, the shortest distance illustrated by the letter d in Figure 1 which is located between a part of the proximal end (3a) of the supply means (3) and the inclined wall (6) of the sedimentation means (2) can define a section dx (illustrated in hatching in Figure 2) or dx' (not illustrated) which extends all around the internal wall of said sedimentation means and which thus defines a total surface.

[0165] Example 1 - Figure 1

[0166] Figure 1 illustrates a first embodiment of the device according to the invention which makes it possible to produce organometallic compounds. This constitutes Example 1.

[0167] The device has a feed airlock which contains a free space (at the level of ref. 1 1 ) for said substrate 9 (before introduction into the reactor), said airlock being located above said sedimentation means 2. Said feed airlock being actuable by means of a system comprising a series of valves 1 1 , in this case 3 valves. The free space is filled with an inert gas (here, nitrogen). Between 2 valves a free space is created which contains the gas and which makes it possible to create an airlock into which the substrate 9 can be introduced.

[0168] The reactor 1 has an inlet 12 located at a first end 1a downstream of the reactor 1.

[0169] The sedimentation means 2 is connected to the second end 1 b of said reactor 1 , opposite said first end of said reactor 1 a. The end 1 b is also that at the angle y. The sedimentation means 2 accommodates a supply means 3. The supply means 3 extends partly inside said sedimentation means 2 and partly outside it, and has a longitudinal shape which is parallel to said internal face 7 of the reactor 1. The proximal end 3 a of said supply means 3, which is adjacent to the inclined wall 6 of the sedimentation means, is located inside said sedimentation means 2 and the distal end 3 b, opposite the proximal end 3 a, is located outside said sedimentation means 2.

[0170] Said sedimentation means 2 comprises an inclined internal wall 6 which forms an angle y, with an internal face 7 of said reactor 1, of a value greater than 180°.

[0171] Said supply means 3 has at one of its ends an opening which has a section X and in that the reactor has a section Y which is greater than or equal to the section X.

[0172] The sedimentation means 2 has a first narrow open end and a second wider closed end (compared to the first end). More precisely, the first end has a section A smaller than the section B of the second closed end of said sedimentation means. The first open end is oriented facing the second end of the reactor 1, preferably rests (is aligned) on the periphery of the reactor 1. This connection between the sedimentation means 2 and the reactor 1 is watertight.

[0173] Said sedimentation means 2 comprises a rising speed homogenization element 8 which is in the form of a perforated plate 8 which extends on either side of said supply means 3.

[0174] The proximal end 3a of said supply means is adjacent to said inclined internal wall 6 of said sedimentation means and is separated therefrom by a distance d sufficient to allow a reduction in the upward speed of said fluid during its passage through said sedimentation means 2 towards said outlet 5 of said device.

[0175] Thus, the shortest distance between the proximal end 3a of the supply means 3 and the inclined wall 6 of the sedimentation means 2 defines the section dx which extends all around the internal wall of the sedimentation means 2 and which defines a total surface.

[0176] The end 3a', which is diametrically opposite the proximal end 3a of the supply means 3, is adjacent to said inclined internal wall 6' of said sedimentation means 2 and is separated therefrom by a distance d' sufficient to allow a reduction in the upward speed of said fluid during its passage in said sedimentation means 2 towards said outlet 5 of said device.

[0177] The distances d and d' are equal according to this embodiment.

[0178] The recirculation loop 4 comprises an extraction means 4a located upstream of said device, an injection means 4b downstream of said reactor 1, being adjacent to said inlet 12 of said reactor 1, and a thermal regulation means 4c, preferably a heat exchanger 4c located between the injection means 4b and the extraction means 4a. Said extraction means 4a of said recirculation loop 4 is located at the same level as said outlet 5 of said device. The recirculation loop 4 comprises a filtration means (not shown) followed by a recirculation pump (not shown).

[0179] The outlet 5 of the device is located in the upper part of said sedimentation means 2. At the outlet of the device (outside the device) is located a filter (not shown) to separate the substrate 9 from said fluid, so as to prevent the passage of solid particles having a size greater than or equal to 50 μm in the present case.

[0180] As illustrated in Figure 1, the fluid / reagent is present up to a high upper portion of the supply means 3. In this case, the embodiment indicates the presence of a free zone just above the reagent / fluid which is filled with gas.

[0181] The reactor 1 and the sedimentation means 2 are completely filled with said fluid and solvent, when the device operates continuously.

[0182] In operation, the substrate 9 is supplied into the feed lock (at ref. 1 1 ) so as to pass the solid particles 9 into the free space which contains the nitrogen. By the closing / opening system of the valves 1 1 , the solid magnesium particles in this case are poured regularly into the reactor, in order to maintain the level of the bed 9 and continue the process. The reactor is continuously supplied with reactant (vinyl bromide), with THF (tetrahydrofuran), in the opposite direction of flow of the Mg 9 particles, until a fluid is formed which includes a small quantity of the unreacted vinyl bromide and the compound of interest (vinyl magnesium bromide) with the tetrahydrofuran. The recirculation loop 4 operates continuously and allows efficient management of the thermal properties throughout the process.This allows the continuous extraction of said fluid and / or said reagent, cooling or heating thereof and continuous injection of said fluid and / or said reagent, in the opposite direction of flow of said substrate 9.

[0183] Also, the substrate 9 was added into the reactor 1 until more than half of its volume was formed of the bed of solid particles 9, thus leaving a part (volume) of said reactor 1 filled with said reagent and / or said fluid, above said bed 9. The addition is made above the reagent. Indeed, ref. 1 Ob represents the min level of fluid / reagent in the supply means 3 and ref. 10a represents the maximum level of liquid within the supply means 3.

[0184] The presence of the perforated plate 8 contributes to the homogenization of the upward speed of the fluid in the sedimentation means 2.

[0185] Example 2

[0186] A first test (test 1) is carried out with a device comprising a sedimentation means comprising a supply means (distance “13” equal to 46mm).

[0187] A second test (test 2) is reproduced with the same device, but in the absence of a means of supply (distance “13” equal to zero).

[0188] Here are the parametric conditions of the two tests:

[0189] - Fluid density: 842.64 kg / m 3 (Tetrahydrofuran 60°C);

[0190] - Diameter of the particles considered for the determination of the maximum upward velocity of the fluid in the upper part of the sedimentation means so that the sedimentation velocity of the particles is greater than the upward velocity of the fluid: 50 m;

[0191] - Dynamic viscosity of the fluid: 0.000337 Pa.s;

[0192] - Particle density: 1738 kg / m 3 ;

[0193] - A rising speed of the fluid in reactor 1 of 5 mm / s (recirculation-injection ratio 8:1);

[0194] - A reactor volume of 25 liters;

[0195] - A residence time of between 0.5 and 1 hour. During test 1, the upward velocity of the fluid in the sedimentation means 2 is less than 1.5 mm / s, at the level of the upper part of the sedimentation means.

[0196] In test 2, the upward velocity of the fluid in sedimentation means 2 is greater than 2.25 mm / s, at the upper part of the sedimentation means. In addition, magnesium particles were entrained in the recirculation loop. Such a configuration requires working at a lower fluid and reagent injection rate than initially applied, resulting in a significant loss of production.

[0197] Example 3

[0198] This example illustrates several configurations taking into account the Y and d sections of a type of reactor according to the illustrated examples and which falls within the scope of the present invention.

[0199] Figure 2

[0200] Figure 2 corresponds to a part of the device described in Figure 1 above, except that a hatched area has been indicated to illustrate the section dx (or dx') defined by the distance d.

[0201] In the context of the present invention, any singular article such as, for example, "a", "an", "the", "the", "of", "of the" may be replaced by an article which designates a plural, for example "at least one", "at least 2", "at least 3", "several", etc.

[0202] The word "include", "contains" or any equivalent or derived term may be replaced by "consisting of" in order to define a list or exclusive selection possibilities so as not to include other elements not mentioned in the expression used.

[0203] It is understood that the present invention is in no way limited to the embodiments described above.

Claims

CLAIMS 1. Device for producing orgonometollic compounds comprising: - A reactor (1) arranged to contain a substrate (9) containing a metal and forming a bed of solid particles (9), said reactor (1) comprising, at a first end (la) located downstream thereof, an inlet (12) for continuously supplying said reactor (1) with reagent, and optionally a solvent, - A sedimentation means (2) being connected to said reactor (1), opposite said first end (la) of said reactor (1), and receiving a supply means (3) arranged to deliver said substrate (9) above the bed of solid particles (9), - A recirculation loop (4) which comprises an extraction means (4a) located upstream of said device, an injection means (4b) downstream of said reactor (1) and a thermal regulation means (4c), preferably a heat exchanger (4c), said recirculation loop (4) being arranged to continuously extract a fluid which comprises a part of said reagent and an organometallic compound, cool or heat said fluid and continuously inject it into said reactor (1) by said injection means (4b), - An outlet (5) for said fluid.

2. Device according to claim 1, wherein said sedimentation means (2) comprises an inclined internal wall (6) which forms an angle (y), with an internal face (7) of said reactor (1), of a value greater than 180°, said inclined internal wall (6) relative to said internal face (7) of said reactor (1) being arranged to allow an upward passage of said fluid towards said outlet (5) of said device.

3. Device according to claim 1 or 2, wherein said supply means (3) has a proximal end (3a), at which there is an opening which has a section X and in that the reactor has a section Y which is greater than or equal to said section X.

4. Device according to any one of the preceding claims, wherein said sedimentation means (2) comprises an upward velocity homogenizing element (8) arranged to distribute the upward flows of fluid homogeneously in the sedimentation element and arranged to serve as a filter.

5. Device according to any one of the preceding claims, wherein said outlet (5) of said device is located at said sedimentation means (2), preferably in the upper part thereof.

6. Device according to any one of the preceding claims, wherein said extraction means (4a) of said recirculation loop (4) is located at said sedimentation means (2), preferably at the same level as said outlet (5) of said device, or at the high level of said reactor (1).

7. Device according to any one of the preceding claims, wherein said reactor (1) and said sedimentation means (2) are arranged so that said fluid, optionally in the presence of a solvent, completely covers the bed of solid particles and (completely) fills said reactor (1) and said sedimentation means (2), when the device operates continuously.

8. Device according to any one of the preceding claims, wherein the proximal end (3a) of said supply means (3) is adjacent to said inclined internal wall (6) of said sedimentation means and is separated therefrom by a distance (d) sufficient to allow a reduction in the rate of ascent. of said fluid during its passage through said sedimentation means (2) towards said outlet (5) of said device.

9. Device according to any one of the preceding claims, wherein the proximal end (3a) of the supply means (3) is located at a sufficient distance (13) from the homogenizing element (8) or the outlet (5) of the device or the extraction means (4a) or at the upper edge of the sedimentation means (2).

10. Device according to any one of the preceding claims, wherein the proximal end (3a) of said supply means (3), which is adjacent to said inclined wall (6) of said sedimentation means (2), is located inside said sedimentation means (2). 1 1. A process for producing an organometallic compound comprising the following steps: - Adding a substrate (9) containing a metal upstream of a reactor (1) which is connected to a sedimentation means (2) which accommodates a supply means (3) of said substrate (9), until a bed of solid particles (9) is formed within said reactor (1), - Continuously supplying said reactor (1) with reagent, optionally with a solvent, in the opposite direction of flow of said substrate (9), until a fluid is formed which comprises a part of said reagent and the organometallic compound, - Setting up a recirculation loop (4): continuous extraction of said fluid and / or said reagent, cooling or heating thereof and continuous injection of said fluid and / or said reagent, in the opposite direction of flow of said substrate (9), - Recovery, at the outlet (5) of said device, of said fluid, characterized in that, during the process, said substrate (9) is fed, in the opposite direction to the upward movement of the fluid formed, into said supply means (3), which is partially housed in said sedimentation means (2), in order to deliver said substrate (9) above the bed of solid particles (9) initially formed, and in that said supply means (3) allows a reduction in the upward speed of said fluid formed during reaction, during its passage in said sedimentation means (2), preferably towards the outlet (5) of said device.

12. Method according to claim 10, wherein said rising speed of said fluid in said sedimentation means (2) is at least 1 time, at least 1.5 times, preferably 3 times, more preferably at least 5 times lower than the rising speed of said fluid in said reactor.

13. A method according to claim 10 or 11, wherein the reactor (1) is completely filled with reagent and / or fluid and in that the substrate (9) has been added until more than half of the reactor (1) is formed of said bed of solid particles (9), thus leaving a portion (Z) of said reactor (1) filled with said reagent and / or said fluid, above said bed (9).

14. A method according to any one of claims 10 to 12, wherein said substrate (9) is added above said previously formed bed of solid particles (9), preferably in the reactant and / or fluid present above said bed (9), during the reaction process.

15. Method according to any one of claims 10 to 13, in which the ratio between the volume flow rate of said fluid of the recirculation loop and the volume flow rate of said reagent (optionally in the presence of said solvent) added to the reactor is between 1:1 and 500:1, preferably between 1:1 and 70:1 16. A method for producing an organometallic compound, being carried out in a device according to any one of claims 1 to 9, comprising the following steps: Adding a substrate (9) containing a metal upstream of said reactor (1) until a bed of solid particles (9) is formed within said reactor (1), Continuously supplying said reactor (1) with reagent, optionally with a solvent, in the opposite direction of flow of said substrate (9), until a fluid is formed which comprises a part of said reagent and the organometallic compound, Setting up a recirculation loop (4): continuous extraction of said fluid and / or said reagent, cooling or heating thereof, and continuous injection of said reagent and / or fluid, in the opposite direction of flow of said substrate, Recovery, at the outlet (5) of said device, of said fluid, characterized in that, during the process, said substrate (9) is fed, in the opposite direction to the upward movement of the fluid formed, into said supply means (3), which is partially housed in said sedimentation means (2), in order to deliver said substrate (9) above the bed of solid particles initially formed, and in that said supply means (3) allows a reduction in the upward speed of said fluid formed during the reaction, during its passage through said sedimentation means (2), preferably towards the outlet (5) of said device.

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