Process for oligomerization in a reactor comprising a gas / liquid dual distributor

Abstract

This invention relates to a gas / liquid reactor for oligomerizing gaseous ethylene, comprising a gaseous ethylene injection device and a liquid injection device, the injection device being advantageously arranged such that the injection of the liquid can cause a reduction in the size of the ethylene bubbles through shearing during the injection of the gaseous ethylene. The gas / liquid reactor according to the invention can be used for injecting any gaseous olefin feedstock into the liquid phase.

Description

Technical Field

[0001] This invention relates to the technical field of gas / liquid reactors for oligomerizing olefins into linear olefins via homogeneous catalysis.

[0002] The present invention also relates to the use of the gas / liquid reactor in a process for oligomerizing gaseous olefin feedstocks, preferably gaseous ethylene, to produce linear α-olefins or mixtures of several linear α-olefins such as 1-butene, 1-hexene or 1-octene. Background Technology

[0003] This invention relates to the technical field of gas / liquid reactors, also known as bubble columns, and further to their use in processes for the oligomerization of olefin feedstocks, preferably ethylene. One disadvantage encountered when using such a reactor in an ethylene oligomerization process is the management of the gas headspace, which corresponds to the upper portion of the reactor in the gaseous state. The gas headspace comprises gaseous compounds slightly soluble in the liquid phase, partially soluble but inert compounds in the liquid, and gaseous ethylene insoluble in the liquid. The transfer of gaseous ethylene from the lower liquid portion of the reaction chamber to the gas headspace is a phenomenon known as breakthrough. In practice, the gas headspace is vented to remove the gaseous compounds. When the amount of gaseous ethylene present in the gas headspace is high, venting the gas headspace results in a non-negligible loss of ethylene, which is detrimental to the productivity and cost of the oligomerization process. Furthermore, significant breakthrough means that a large amount of gaseous ethylene has not yet dissolved in the liquid phase and therefore cannot react, which is detrimental to the productivity and selectivity of the oligomerization process.

[0004] To improve the efficiency of oligomerization processes, particularly in terms of productivity and cost, it is crucial to limit ethylene breakthrough in order to increase its conversion in the process while maintaining good selectivity for the desired linear α-olefins.

[0005] Use such as Figure 1 The existing technology for the gas / liquid reactor illustrated in the figure cannot limit the loss of gaseous ethylene, and the purging of the gas headspace causes gaseous ethylene to leave the reactor, which is detrimental to the yield and cost of the process.

[0006] In patent applications WO 2019 / 011806 and WO 2019 / 011609, the applicant describes processes that increase the contact surface area between the upper portion of the liquid phase and the gas headspace through a dispersion device or eddy current, thereby promoting the transfer of ethylene contained in the gas headspace towards the liquid phase at the liquid / gas interface. These processes fail to limit permeation and are inadequate when the amount of ethylene in the gas headspace is large due to high permeation levels.

[0007] Furthermore, during their research, the applicant discovered that in a reactor operating at a constant flow rate of injected gaseous ethylene, the amount of dissolved ethylene and the breakthrough phenomenon depend on the size of the injected gaseous ethylene bubbles. The time required for gaseous ethylene to dissolve in the liquid phase corresponds to the travel time of the bubbles in the liquid height, which is determined by the operating conditions and the height of the reactor. The amount of gaseous ethylene dissolved per unit time is proportional to the contact area between the gas and liquid phases. Larger bubbles have a lower area / volume ratio and require a longer dissolution time, which increases the breakthrough phenomenon for a given liquid phase height.

[0008] The applicant has discovered that the conversion of one or more olefins can be improved by limiting breakthrough through a specific gas / liquid reactor for oligomerization of gaseous olefin feedstocks (particularly gaseous ethylene), while simultaneously maintaining high selectivity for the desired linear olefins (one or more), and particularly for α-olefins (one or more), wherein the gas / liquid reactor comprises a gaseous ethylene injection device and a liquid injection device, the injection device being advantageously arranged such that the injection of the liquid causes a reduction in the ethylene bubble size by shearing during the injection of gaseous ethylene. The gas / liquid reactor according to the invention can be used for any gaseous olefin feedstock injected into the liquid phase. Summary of the Invention

[0009] The present invention relates to a gas / liquid reactor for oligomerization of gaseous olefin feedstock, comprising a gas injection device (3) and a liquid injection device (12), the injection devices being arranged such that the injection of liquid can cause a reduction in bubble size by shearing during the injection of the gaseous olefin feedstock.

[0010] Preferably, the gas injection device (3) includes at least one gas injection orifice, and the liquid injection device (12) includes at least one liquid injection orifice, each gas injection orifice being located near the orifice of the liquid injection device (11) and positioned such that the gas injection trajectory is in the plane of the liquid injection trajectory.

[0011] Preferably, the liquid injection orifice and the gas injection orifice are circular, and the diameter of the liquid injection orifice is greater than or equal to the diameter of the gas injection orifice.

[0012] Preferably, at least one gas injection orifice and at least one liquid injection orifice are positioned so that they face each other at an angle between 0° and 180°.

[0013] Preferably, the gas injection device and the liquid injection device are selected from pipes, nets made of pipes, multi-pipe distributors, perforated plates, cylindrical pipes and concentric pipes.

[0014] Preferably, the gas injection device is a cylindrical tube in the form of an annular ring with injection orifices, and the liquid injection device is a cylindrical tube in the form of an annular ring with injection orifices.

[0015] Preferably, the diameter of the annular gas injection device is smaller than the diameter of the annular liquid injection device, and the gas injection device is positioned inside the liquid injection device on different planes.

[0016] Preferably, a series of liquid and gas injection devices in the form of a ring with decreasing diameter alternate from the periphery to the center, represented by the central axis of the device with the largest diameter. The devices are positioned such that the gas injection orifice of the gas injection device is positioned close to the orifice of the adjacent liquid injection device, such that the liquid injection trajectory and the gas injection trajectory are in the same plane, thereby causing shearing of the gas.

[0017] Preferably, the orifices of the gas injection device and the liquid injection device each extend through pipes (13, 15).

[0018] Preferably, the diameter of the tube (13) of the gas injection device (3) is smaller than the diameter of the tube (15) of the liquid injection device (12), and the opening outlet end of the tube (13) of the gas injection device (3) is coaxially positioned inside the liquid injection tube.

[0019] Preferably, the liquid injection pipe (15) includes a deflector.

[0020] Preferably, the end of the liquid injection pipe (15) has a tapered portion with a tapered outlet diameter.

[0021] Preferably, the reactor further includes

[0022] - A reaction chamber, the reaction chamber having an elongated shape along a vertical axis, the reaction chamber being capable of including

[0023] The system comprises a liquid phase in a lower region and a gaseous phase in an upper region above the lower region. The liquid phase includes reaction products, dissolved and gaseous olefin feedstock (preferably dissolved and gaseous ethylene), a catalytic system, and optionally a solvent, and preferably consists thereof. The gaseous phase includes gaseous olefin feedstock (preferably gaseous ethylene) and non-condensable gases (particularly ethane).

[0024] - A device for introducing the catalytic system, the device being located in the lower portion of the reaction chamber.

[0025] - A recirculation loop, the recirculation loop comprising an extraction device at the base (preferably, the bottom) of the reaction chamber for extracting a portion of the liquid, a heat exchanger for cooling the liquid, and an introduction device for introducing the cooled liquid, the introduction device being located in the upper portion of the lower region of the reaction chamber.

[0026] - and optionally, a gas phase recovery loop for recovering at least a portion of the gas phase to the lower region of the liquid phase, the gas phase recovery loop including an extraction device located in the upper region of the reaction chamber to extract a gas portion of the gas phase and an introduction device located in the lower region of the reaction chamber to introduce the extracted gas portion into the liquid phase.

[0027] Another subject of the invention relates to a process for oligomerizing gaseous olefin feedstock using a gas / liquid reactor as previously defined, the process comprising contacting a liquid comprising a catalytic system with the gaseous olefin feedstock by means of a gas injection device and a liquid injection device, the catalytic system comprising a metal catalyst, at least one activator and at least one additive and optionally a solvent, the injection device being arranged such that the injection of the liquid causes a reduction in the size of the gaseous ethylene bubbles through shearing.

[0028] Preferably, the gaseous olefin feedstock comprises 2 to 6 carbon atoms, and more preferably, comprises 2 to 4 carbon atoms.

[0029] Preferably, the injection velocity of the liquid is greater than the injection velocity of the gaseous olefin feedstock, thereby promoting the shearing of the olefin bubbles into smaller bubbles.

[0030] Definitions and abbreviations

[0031] Throughout this specification, the following terms or abbreviations have the following meanings.

[0032] The term "oligomery" refers to any addition reaction from a first olefin to a second olefin, which may be the same as or different from the first olefin. The resulting olefin has the empirical formula C0. n H 2n , where n is equal to or greater than 4.

[0033] The term "linear α-olefin" refers to an olefin in which the double bond is located at the end of a linear alkyl chain.

[0034] The term "catalytic system" refers to a class of chemicals that enable the use of a catalyst. This catalytic system can be a metal precursor comprising one or more metal atoms or a mixture of compounds for catalyzing a chemical reaction, and more specifically, for catalyzing the oligomerization of olefins. The mixture of compounds includes at least one metal precursor. The mixture of compounds may also include an activator. The mixture of compounds may include additives. The compounds or mixtures of compounds may optionally be present in a solvent.

[0035] The term "liquid phase" refers to a mixture of all compounds in a liquid physical state under the temperature and pressure conditions of a reaction chamber.

[0036] The term "gas phase" refers to a mixture of all compounds in a gaseous physical state under the temperature and pressure conditions of the reaction chamber: existing in the liquid as bubbles and also in the top part of the reactor (or the gas headspace of the reactor).

[0037] The term "lower region of the reaction chamber" refers to the portion of the chamber that includes the liquid phase, the gaseous olefin feedstock (particularly gaseous ethylene, advantageously in bubble or dissolved form), reaction products such as the desired linear α-olefin (i.e., 1-butene, 1-hexene, 1-octene, or a mixture of several linear α-olefins), the catalytic system, and optionally the solvent. Preferably, the lower region of the reaction chamber occupies at least half, and more preferably three-quarters, of the total volume of the reaction chamber.

[0038] The term "upper region of the reaction chamber" refers to the portion of the chamber located at its apex, that is, directly above the lower region, and includes the gas phase corresponding to the gas top space.

[0039] The term "non-condensable gas" refers to a gaseous physical form that is only partially soluble in the liquid under the temperature and pressure conditions of the reaction chamber and can accumulate in the headspace of the reactor under certain conditions (e.g., ethane here).

[0040] The terms “reactor” or “device” refer to all apparatuses that enable the implementation of the oligomerization process according to the invention, particularly such as reaction chambers and recycling loops.

[0041] The term "lower part of the reaction chamber" refers to the lower quarter of the lower region of the reaction chamber that contains the liquid phase.

[0042] The term "upper part of the reaction chamber" refers to the upper quarter of the reaction chamber and is part of the lower region intended to contain the liquid phase.

[0043] The expression “saturation of dissolved gaseous olefin feedstock, particularly dissolved ethylene” refers to the ratio of the amount of dissolved gaseous olefin feedstock (particularly dissolved ethylene) to the maximum amount of dissolved gaseous olefin feedstock (particularly ethylene) that can dissolve in a liquid under the temperature and pressure conditions considered.

[0044] The various components of the reactor will be described with reference to all the accompanying drawings, and each component will maintain the same reference numerals across different drawings. Attached Figure Description

[0045] Figure 1 The diagram illustrates a reactor according to the prior art. This reactor includes a reaction chamber 1 and means for introducing gaseous olefin feedstock 2 (specifically, gaseous ethylene) into the liquid phase via a gas injection device 3. The reaction chamber 1 includes a lower region containing the liquid phase and an upper region containing the gas phase. The gas phase in the upper portion of the reaction chamber 1 includes a venting device 4. A pipe for extracting the liquid portion 5 is located at the bottom of the reaction chamber 1. This portion 5 is divided into two streams: a first main stream 7, which is sent to a heat exchanger 8 and then introduced into the liquid phase via a pipe 9, and a second stream 6, corresponding to the effluent sent to a later step. A pipe 10 at the bottom of the reaction chamber facilitates the introduction of a catalytic system.

[0046] Figure 2 This reactor is described according to the invention. This reactor differs from... Figure 1 The reactor is characterized in that the stream leaving the heat exchanger 8 is split into two streams 9 and 11, and stream 11 is sent to the liquid region of the same chamber 1 via a liquid injection device 12 arranged together with the gas injection device 3, such that the injection of liquid can cause the ethylene bubble size to decrease by shearing during the introduction of gaseous ethylene and stream 11.

[0047] Figure 3A This is a schematic diagram along the vertical axis of a chamber (which may be above or below) according to an embodiment of the gas injection device 3 and liquid injection device 12 arranged in the reaction chamber 1. The gas injection device 3 and liquid injection device 12 have a circular shape and are arranged such that a plurality of gas outlet orifices inject gas toward the outer wall of the chamber 1, wherein each gas outlet orifice extends through a tube 13 of the gas injection device 3, and the gas injection trajectory passes perpendicularly through the trajectory of the liquid injection orifice 14, thereby causing gas shearing to reduce the bubble size of the injected gas.

[0048] Figure 3B It is along Figure 3A A schematic diagram of the cross-section of the vertical axis of the injection device. The liquid injection device 12 is a ring with a diameter larger than that of the gas injection device 3, which itself is also ring-shaped. The liquid injection device 12 and the gas injection device 3 are positioned on different planes. Figure 3BIn this configuration, the liquid device 12 is located on a plane below the plane of the gas injection device 3, such that the orifice of the gas injection device 3 is positioned on the trajectory of the orifice 14 of the liquid injection device 12.

[0049] Figure 3C It is along according to Figure 3A A schematic diagram of the cross-section of the vertical axis of the injection device, illustrating the shearing effect of the liquid flow injected by the liquid injection device 12 on the gas flow injected by the gas injection device 3.

[0050] Figure 4 This is a schematic cross-section along the vertical axis, illustrating a variation in the arrangement of the gas injection device 3 and the liquid injection device 12. In this variation, the gas injection orifice extends through pipe 13, and similarly, the liquid injection orifice 14 extends through pipe 15. The gas injection pipe 13 has a curvature of 90°, and the open end of pipe 13 is concentrically positioned inside pipe 15 for extending the injection orifice 14 of the liquid injection device 12. The open end of gas injection pipe 13 is positioned at the center of liquid injection pipe, and the gas outlet is located at this open end. Therefore, the gas jet and liquid jet are oriented in the same direction, and the shearing of the liquid on the gas is obtained through the encapsulation and stripping of the gas by the liquid.

[0051] Figure 5A Illustration Figure 4 A variation of the embodiment includes positioning the deflector 16 at the end of the liquid jet pipe 15. The obstruction of the gas-liquid flow entrained by the deflector at the outlet of the device allows for improved bubble shearing by generating additional turbulence, which in turn improves the breakdown of the bubble into smaller bubbles.

[0052] Figure 5B Illustration Figure 4 A variation of the embodiment includes a taper 17 at the end of the liquid injection tube 15. This taper causes acceleration of the gas-liquid mixture during injection, which increases shear and thus promotes the breakdown of bubbles into smaller bubbles. Detailed Implementation

[0053] It is clear that throughout the entire text of this specification, the phrase "between... and..." should be understood to include the extreme values ​​mentioned.

[0054] Within the meaning of this invention, the various embodiments presented can be used alone or in combination with each other, but there are no limitations on the combination.

[0055] For the purposes of this invention, various parameter ranges (such as pressure ranges and temperature ranges) for a given step can be used individually or in combination. For example, for the purposes of this invention, it is preferred that the pressure range be combined with a more preferred temperature range.

[0056] Throughout this specification and claims, the positions of the elements (“bottom”, “top”, “above”, “below”, “horizontal”, “vertical”, “lower half”, etc.) are defined relative to the tower in its operating position.

[0057] The present invention relates to a gas / liquid reactor for oligomerization of gaseous olefin feedstock, comprising a gas injection device and a liquid injection device, the injection device being arranged such that the liquid injection can cause a reduction in the bubble size of the gaseous olefin feedstock by shearing during the injection of the feedstock.

[0058] For the purposes of this invention, the gas injection device is designed to inject gaseous olefin feedstock into the oligomerization reactor.

[0059] Advantageously, the reactor according to the invention allows for improved solubility of gaseous olefins in the liquid phase containing the catalytic system and reduces the rising velocity of gaseous olefins in the liquid phase, which synergistically reduces breakthrough. Specifically, the smaller the injected gaseous olefin bubbles, the lower their rising velocity in the liquid phase.

[0060] Advantageously, the dissolved gaseous olefin feedstock (particularly, the dissolved ethylene) has a saturation of more than 70.0% in the liquid phase, preferably between 70.0% and 100%, preferably between 80.0% and 100%, preferably between 80.0% and 99.0%, preferably between 85.0% and 99.0%, and even more preferably between 90.0% and 98.0%.

[0061] The saturation of dissolved gaseous olefins (preferably dissolved gaseous ethylene) can be measured by any method known to those skilled in the art, such as by gas chromatography (commonly referred to as GC) analysis of a portion of the liquid phase extracted from the reaction chamber.

[0062] Another advantage of the present invention is that it improves the conversion rate of olefin feedstocks, especially ethylene, and / or the selectivity for olefins (especially α-olefins), as well as the unit volume productivity of oligomerization processes.

[0063] Therefore, another advantage of the reactor according to the invention is that, for the same performance, it allows for a reduction in reaction volume and thus a reduction in reactor size, compared to reactors according to the prior art.

[0064] reactor

[0065] The present invention relates to a gas / liquid reactor for oligomerization of gaseous olefin feedstock, comprising a gas injection device and a liquid injection device, the injection device being arranged such that the injection of liquid can cause a reduction in bubble size by shearing during the injection of the gaseous olefin feedstock.

[0066] The shearing effect of the liquid flow on the gas flow allows for the decomposition of bubbles, thereby reducing their size and thus improving their solubility in the liquid phase. Therefore, the arrangement of the gas injection device and the liquid injection device according to the invention allows for the reduction of bubble size, preferably gaseous ethylene, to accelerate the dissolution of the gas (preferably gaseous ethylene) in the liquid phase.

[0067] Preferably, the gas / liquid oligomerization reactor is a gas / liquid reactor for the dimerization, trimerization, or tetramerization of ethylene.

[0068] The gas injection device 3 includes at least one gas injection orifice, and the liquid injection device 12 includes at least one liquid injection orifice. Each gas injection orifice is located near the orifice of the liquid injection device 11 and is positioned such that the gas injection trajectory lies in the plane of the liquid injection trajectory. The liquid injection then causes shearing of the injected gas and results in a reduction in bubble size, thereby improving the solubility of the gas in the liquid phase by increasing the gas-liquid interface.

[0069] It should be understood that, for the purposes of this invention, the gas injection device and the liquid injection device may include multiple orifices for injecting gas and liquid, respectively, depending on the size of the reactor.

[0070] Advantageously, the reactor according to the invention, having a specific arrangement of gas injection devices and liquid injection devices, allows the size of the injected bubbles to be reduced by at least 20% relative to the size of the injected bubbles in the absence of shear. Preferably, the percentage reduction in bubble size due to shear is at least 25% relative to the size of the injected bubbles in the absence of shear, preferably at least 30%, more preferably at least 35%, and most preferably at least 40%.

[0071] Advantageously, breaking down a bubble into two smaller bubbles of the same size increases the exchange area between the gas and liquid by 26%, breaking it down into four smaller bubbles of the same size causes an increase of 59%, and breaking it down into six smaller bubbles of the same size causes an increase of 82%. Therefore, the reactor according to the invention promotes and thus significantly improves the absorption of gas in the liquid phase, which allows for increased saturation of the gaseous olefin feedstock in the liquid phase and limits breakthrough.

[0072] Preferably, the gas injection device 3 is selected from pipes, a network of pipes, a multi-pipe distributor, a perforated plate, a cylindrical pipe, a concentric pipe, or any other device known to those skilled in the art.

[0073] The term "jet orifice" refers to an inverted orifice, oval orifice, slit, or any other form used to inject liquid or gas into a reactor.

[0074] Preferably, the gas injection orifice is circular, i.e., rounded. Preferably, the gas injection orifice has a diameter between 1.0 and 20.0 mm, more preferably between 3.0 and 15.0 mm, so as to form ethylene bubbles with millimeter dimensions in the liquid.

[0075] Preferably, the liquid injection orifice has a diameter between 1.0 and 15.0 mm, more preferably between 3.0 and 20.0 mm.

[0076] Preferably, the liquid injection orifice is circular, i.e., rounded. Preferably, both the gas injection orifice and the liquid injection orifice are circular, and the diameter of the liquid injection orifice is greater than or equal to the diameter of the gas injection orifice. Preferably, the ratio of the diameter of the gas injection orifice to the diameter of the liquid injection orifice disposed near the gas injection orifice is between 0.1 and 1.0, preferably between 0.4 and 0.8.

[0077] In a preferred embodiment, the orifices of the gas injection device and / or the liquid injection device extend through pipes. Preferably, the orifices of the gas injection device and the liquid injection device extend through pipes, and the diameter of the gas injection pipe 13 of the gas injection device is smaller than the diameter of the pipe of the liquid injection device 15. The opening outlet end of each gas injection pipe 13 is preferably coaxially positioned inside the liquid injection pipe. The outlet orifice of the gas injection pipe points towards the outlet orifice of the liquid injection pipe.

[0078] Preferably, the liquid injection pipe 15 includes a deflector as a device for partially closing the pipe, preferably a circular or square plate, which may or may not be perforated, such as... Figure 5A As illustrated in the figure. Advantageously, this deflector allows for improved shearing action of the liquid on the bubbles.

[0079] Preferably, the outlet end of the liquid injection pipe has a tapered portion in terms of outlet diameter, such as... Figure 5B As illustrated in the figure. The tapering section causes acceleration of the gas-liquid mixture, which allows for increased shear force and further improves the decomposition of bubbles into smaller bubbles.

[0080] In a highly preferred embodiment, the tube has a tapered section of the outlet diameter and a deflector.

[0081] Preferably, the apparatus for injecting gas (preferably gaseous ethylene) and liquid is located in the reaction chamber, preferably in the lower part.

[0082] Advantageously, the gas injection orifice and the liquid injection orifice are positioned facing each other at an angle between 0° and 180°. When the orifices of the gas injection device and the liquid injection device extend through the pipe, the gas injection orifice and the liquid injection orifice correspond to the outlet orifices of the gas injection pipe and the liquid injection pipe, respectively. A 0° angle means that the gas and liquid are injected via the corresponding injection orifice along the same trajectory axis and in the same direction, such as... Figure 4 As illustrated in the figure. Preferably, the angle formed by the trajectory is between 0° and 120°, more preferably between 30° and 120°, and even more preferably between 45° and 90°. Very preferably, the angle formed by the trajectory is between 0° and 90°. Preferably, the angle formed by the trajectory is equal to 0°, 30°, 45°, 90°, 120°, or 180°.

[0083] In a particular embodiment, the gas injection device is a cylindrical tube with an annular shape, such as a rounded or oval shape, and has injection orifices. Advantageously, the liquid injection device is also a cylindrical tube with a generally annular shape, such as a rounded or oval shape, and has injection orifices. According to the invention, the liquid injection device is positioned close to the gas injection device, and one (or each) gas injection orifice is positioned close to the orifice of the liquid injection device 11, such that the liquid injection trajectory and the gas injection trajectory are in the same plane, thereby causing shearing of the gas.

[0084] Advantageously, the gas injection device is annular, preferably circular, and its diameter is larger or smaller than the diameter of the annular liquid injection device (preferably circular). When the diameter of the gas injection device is smaller than the diameter of the liquid injection device, the gas injection device is positioned inside the liquid injection device, on a different plane, i.e., above or below it, such as... Figure 3A As illustrated in the diagram. Conversely, when the diameter of the gas injection device is larger than that of the liquid injection device, the gas injection device is positioned outside the liquid injection device, on a different plane, i.e., above or below it.

[0085] In a particular embodiment, a series of liquid and gas injection devices, arranged in a ring with decreasing diameter, alternate from the periphery to the center, which is represented by the central axis of the device with the largest diameter. The devices are positioned relative to each other such that the gas injection orifice of the gas injection device is positioned close to the orifice of the adjacent liquid injection device, such that the liquid and gas injection trajectories lie in the same plane, thereby causing shearing of the gas.

[0086] Specifically, the gas / liquid reactor may also include:

[0087] -Reaction chamber 1, reaction chamber 1 has an elongated shape along a central vertical axis, reaction chamber 1 may include

[0088] The system comprises a liquid phase in the lower region and a gaseous phase in the upper region above the lower region. The liquid phase includes reaction products, dissolved and gaseous olefin feedstock (preferably dissolved and gaseous ethylene), a catalytic system, and optionally a solvent, and preferably consists thereof. The gaseous phase includes gaseous ethylene and non-condensable gases (particularly ethane).

[0089] - A device for introducing the catalytic system, wherein the device may optionally be located in the lower part of the reaction chamber.

[0090] - A recirculation loop comprising an extraction device at the base (preferably, the bottom) of the reaction chamber for extracting a portion of the liquid, a heat exchanger for cooling the liquid, and a device for introducing the cooled liquid, the introduction device being located in the upper portion of the lower region of the reaction chamber.

[0091] - and optionally, a gas phase recovery loop for recovering at least a portion of the gas phase to a lower region of the liquid phase, the gas phase recovery loop including an extraction device located in the upper region of the reaction chamber to enable extraction of a gas portion of the gas phase and an introduction device located in the lower region of the reaction chamber to enable introduction of the extracted gas portion into the liquid phase.

[0092] Preferably, reaction chamber 1 is cylindrical. In the case of a cylindrical chamber, the diameter D is the diameter of the cylinder. This geometry, in particular, allows for the containment of the "dead zone" volume within the tower.

[0093] oligomerization process

[0094] Another subject of the invention relates to a process for oligomerization of a gaseous olefin feedstock (preferably, gaseous ethylene) using a gas / liquid reactor as defined above, the process comprising contacting a liquid with the gaseous olefin feedstock (preferably, gaseous ethylene) by means of a gas injection device and a liquid injection device, the injection device being arranged such that the injection of the liquid causes a reduction in the bubble size of the gaseous ethylene by shearing.

[0095] In a moving fluid, any velocity difference within the fluid induces shear stress: faster-moving fluid particles are slowed down by those that move slower. Contact between the gas phase and the liquid phase, whose ejection velocity is higher than that of the gas, induces shear stress at the gas / liquid interface, leading to bubble decomposition. Shear is a consequence of turbulence and can be measured indirectly by measuring the velocity fluctuations of each phase or calculated using methods known to those skilled in the art.

[0096] Preferably, the injection velocity of the liquid is greater than the injection velocity of the gaseous olefin feedstock, thereby promoting bubble shearing and reducing the size of the olefin bubbles to smaller bubbles.

[0097] Preferably, the jet velocity of the liquid is between 0.1 and 20 m / s, and the jet velocity of the gas is between 1.0 and 10 m / s.

[0098] The process of oligomerizing gaseous olefin feedstock using the reactor according to the invention enables the production of linear α-olefins by contacting the olefin feedstock with a catalytic system, optionally in the presence of a solvent.

[0099] The gaseous olefin feedstock preferably comprises 2 to 6 carbon atoms, more preferably 2 to 4 carbon atoms. Preferably, the olefin feedstock is selected from butene, more particularly isobutene or 1-butene, propylene, and ethylene, used alone or as a mixture.

[0100] All catalytic systems known to those skilled in the art and applicable to dimerization, trimerization, or tetramerization processes, and more generally applicable to oligomerization processes according to the present invention, fall within the scope of this invention. The catalytic systems and embodiments thereof are described in particular in patent applications FR 2984 311, FR 2 552 079, FR 3 019 064, FR 3 023 183, FR 3 042 989, or patent application FR 3 045414.

[0101] Preferably, the catalytic system comprises, and more preferably consists of, the following:

[0102] - Metallic precursors, preferably based on nickel, titanium, or chromium.

[0103] -Optionally, activator,

[0104] -Optional, additives, and

[0105] -Optional, solvent.

[0106] Metal precursor

[0107] The metal precursors used in the catalytic system are selected from nickel-, titanium-, or chromium-based compounds.

[0108] In one embodiment, the metal precursor is nickel-based and preferably comprises nickel (+II) in an oxidized state. Preferably, the nickel precursor is selected from nickel carboxylate (II), such as nickel 2-ethylhexanoate, nickel phenolate (II), nickel naphthenate (II), nickel acetate (II), nickel trifluoroacetate (II), nickel trifluoromethanesulfonate (II), nickel acetylacetone (II), nickel hexafluoroacetylacetone (II), π-allyl chloride nickel (II), π-bromoallyl nickel (II), methylallyl chloride nickel (II) dimer, η 3 -Allyl nickel hexafluorophosphate, η 3-Methylhexafluorophosphate allyl nickel (II) and 1,5-cyclooctadienyl nickel (II) are used, either alone or as a mixture, in their hydrated or non-hydrated forms.

[0109] In the second embodiment, the metal precursor is based on titanium and preferably includes titanium aryloxy or alkoxy compounds.

[0110] Titanoalkoxy compounds advantageously correspond to the general formula [Ti(OR)4], where R is a linear or branched alkyl radical. Among preferred alkoxy radicals, non-limiting examples that may be mentioned include tetraethoxy, tetraisopropoxy, tetra(n-butoxy), and tetra(2-ethylhexyloxy).

[0111] Titanium aryloxy compounds advantageously correspond to the general formula [Ti(OR')4], where R' is an aryl radical that is either unsubstituted or substituted with an alkyl or aryl group. The radical R' may include substituents based on heteroatoms. The preferred aryloxy radical is selected from phenoxy, 2-methylphenoxy, 2,6-dimethylphenoxy, 2,4,6-trimethylphenoxy, 4-methylphenoxy, 2-phenylphenoxy, 2,6-diphenylphenoxy, 2,4,6-triphenylphenoxy, 4-phenylphenoxy, 2-(tert-butyl)-6-phenylphenoxy, 2,4-di(tert-butyl)-6-phenylphenoxy, 2,6-diisopropylphenoxy, 2,6-di(tert-butyl)phenoxy, 4-methyl-2,6-di(tert-butyl)phenoxy, 2,6-dichloro-4-(tert-butyl)phenoxy, and 2,6-dibromo-4-(tert-butyl)phenoxy, biphenyloxy radical, dinaphthoxy, and 1,8-naphthyldioxy.

[0112] According to a third embodiment, the metal precursor is chromium-based and preferably includes chromium (II) salts, chromium (III) salts, or salts of different oxidation states, which may include one or more identical or different anions, such as halides, carboxylates, and acetylacetone, or alkoxy or aryloxy anions. Preferably, the chromium-based precursor is selected from CrCl3, CrCl3 (tetrahydrofuran)3, Cr (acetylacetone)3, Cr (cycloalkanoic acid)3, Cr (2-ethylhexanoic acid)3, and Cr (acetic acid)3.

[0113] The concentration of nickel, titanium, or chromium is between 0.001 and 300.0 ppm relative to the mass of the reaction, in terms of the mass of atomic metals, preferably between 0.002 and 100.0 ppm relative to the mass of the reaction, more preferably between 0.003 and 50.0 ppm, more preferably between 0.05 and 20.0 ppm, and even more preferably between 0.1 and 10.0 ppm.

[0114] Activator

[0115] Alternatively, without considering metal precursors, the catalytic system includes one or more activators selected from aluminum-based compounds, such as methyl aluminum dichloride (MeAlCl2), dichloroethyl aluminum (EtAlCl2), trichlorotriethyl aluminum complex (Et3Al2Cl3), diethyl aluminum chloride (Et2AlCl), diisobutyl aluminum chloride (i-Bu2AlCl), triethyl aluminum (AlEt3), tripropyl aluminum (Al(n-Pr)3), triisobutyl aluminum (Al(i-Bu)3), diethylethoxyaluminum (Et2AlOEt), methyl aluminum oxane (MAO), ethyl aluminum oxane, and modified methyl aluminum oxane (MMAO).

[0116] additive

[0117] Optionally, the catalytic system includes one or more additives.

[0118] The additive is selected from monodentate phosphorus compounds, bidentate phosphorus compounds, tridentate phosphorus compounds, olefins, aromatic compounds, nitrogen-containing compounds, bipyridine, diimine, monodentate ether, bidentate ether, monodentate sulfide, bidentate sulfide, monodentate or bidentate carbene, and mixed ligands such as phosphopyridine, iminopyridine, and bis(imino)pyridine.

[0119] In the case of a nickel-based catalytic system, the additives are selected from:

[0120] - Nitrogen-containing compounds, such as trimethylamine, triethylamine, pyrrole, 2,5-dimethylpyrrole, pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2-methoxypyridine, 3-methoxypyridine, 4-methoxypyridine, 2-fluoropyridine, 3-fluoropyridine, 3-trifluoromethylpyridine, 2-phenylpyridine, 3-phenylpyridine, 2-benzylpyridine, 3,5-dimethylpyridine, 2,6-di(tert-butyl)pyridine and 2,6-diphenylpyridine, quinoline, 1,10-phenanthroline, N-methylpyrrole, N-butylpyrrole, N-methylimidazolium, N-butylimidazolium, 2,2'-bipyridine, N,N'-dimethylpyridine N,N'-di(tert-butyl)ethane-1,2-diimide, N,N'-di(tert-butyl)butane-2,3-diimide, N,N'-diphenylethane-1,2-diimide, N,N'-bis(2,6-dimethylphenyl)ethane-1,2-diimide, N,N'-bis(2,6-diisopropylphenyl)ethane-1,2-diimide, N,N'-diphenylbutane-2,3-diimide, N,N'-bis(2,6-dimethylphenyl)butane-2,3-diimide or N,N'-bis(2,6-diisopropylphenyl)butane-2,3-diimide, or

[0121] - Phosphine compounds, independently selected from tributylphosphine, triisopropylphosphine, tricyclopentylphosphine, tricyclohexylphosphine, triphenylphosphine, tri(o-tolyl)phosphine, bis(diphenylphosphine)ethane, trioctylphosphine oxide, triphenylphosphine oxide, or triphenyl phosphite, or

[0122] - A compound corresponding to general formula (I) or a tautomer of said compound:

[0123]

[0124] in:

[0125] -A and A' (which may be the same or different) are either oxygen or a single bond between a phosphorus atom and a carbon atom.

[0126] -Group R 1a and R 1b The group is independently selected from methyl, trifluoromethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, cyclohexyl, and adamantyl groups, which may or may not be substituted, and may or may not contain heterogeneous elements; phenyl, o-tolyl, m-tolyl, p-tolyl, isopropylacetone, 3,5-dimethylphenyl, 4-(n-butyl)phenyl, 2-methylphenyl, 4-methoxyphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-isopropoxyphenyl, 4-methoxy-3,5-dimethylphenyl, 3,5-bis(tert-butyl)-4-methoxyphenyl, 4-chlorophenyl, 3,5-bis(trifluoromethyl)phenyl, benzyl, naphthyl, bisnaphthyl, pyridyl, bisphenyl, furanyl, and thiophene groups.

[0127] -Group R 2 The group is independently selected from methyl, trifluoromethyl, ethyl, n-propyl, isopropyl, n-butyl, isobutyl, tert-butyl, pentyl, cyclohexyl, and adamantyl groups, which may or may not be substituted, and may or may not contain heterogeneous elements; phenyl, o-tolyl, m-tolyl, p-tolyl, isopropylacetone, 3,5-dimethylphenyl, 4-(n-butyl)phenyl, 4-methoxyphenyl, 2-methoxyphenyl, 3-methoxyphenyl, 4-methoxyphenyl, 2-isopropoxyphenyl, 4-methoxy-3,5-dimethylphenyl, 3,5-di(tert-butyl)-4-methoxyphenyl, 4-chlorophenyl, 3,5-bis(trifluoromethyl)phenyl, benzyl, naphthyl, bisnaphthyl, pyridyl, bisphenyl, furanyl, and thiophene groups.

[0128] When the catalytic system is titanium-based, the additives are selected from diethyl ether, diisopropyl ether, dibutyl ether, diphenyl ether, 2-methoxy-2-methylpropane, 2-methoxy-2-methylbutane, 2,2-dimethoxypropane, 2,2-bis(2-ethylhexyloxy)propane, 2,5-dihydrofuran, tetrahydrofuran, 2-methoxytetrahydrofuran, 2-methyltetrahydrofuran, 3-methyltetrahydrofuran, 2,3-dihydropyran, tetrahydropyran, 1,3-dioxane, 1,3-dioxane, 1,4-dioxane, dimethoxyethane, bis(2-methoxyethyl) ether, benzofuran, glycol dimethyl ether, and diethylene glycol dimethyl ether, used alone or as a mixture.

[0129] When the catalytic system is based on chromium, the additives are selected from:

[0130] - Nitrogen-containing compounds, such as trimethylamine, triethylamine, pyrrole, 2,5-dimethylpyrrole, pyridine, 2-methylpyridine, 3-methylpyridine, 4-methylpyridine, 2-methoxypyridine, 3-methoxypyridine, 4-methoxypyridine, 2-fluoropyridine, 3-fluoropyridine, 3-trifluoromethylpyridine, 2-phenylpyridine, 3-phenylpyridine, 2-benzylpyridine, 3,5-dimethylpyridine, 2,6-di(tert-butyl)pyridine and 2,6-diphenylpyridine, quinoline, 1,10-phenanthroline, N-methylpyrrole, N-butylpyrrole, N-methylimidazolium, N-butylimidazolium, 2,2'-bipyridine, N,N'-dimethylpyridine N,N'-di(tert-butyl)ethane-1,2-diimide, N,N'-di(tert-butyl)butane-2,3-diimide, N,N'-diphenylethane-1,2-diimide, N,N'-bis(2,6-dimethylphenyl)ethane-1,2-diimide, N,N'-bis(2,6-diisopropylphenyl)ethane-1,2-diimide, N,N'-diphenylbutane-2,3-diimide, N,N'-bis(2,6-dimethylphenyl)butane-2,3-diimide or N,N'-bis(2,6-diisopropylphenyl)butane-2,3-diimide, or

[0131] -The general formula is [M(R)] 3 O) 2-n X n ] y aryloxy compounds, wherein:

[0132] *M is selected from magnesium, calcium, strontium, and barium, with magnesium being preferred.

[0133] *R 3 It is an aryl radical containing 6 to 30 carbon atoms, and X is a halogen or an alkyl radical containing 1 to 20 carbon atoms.

[0134] *n is an integer that can take the values ​​0 or 1, and

[0135] *y is an integer between 1 and 10; preferably, y is equal to 1, 2, 3 or 4.

[0136] Preferably, the aryloxy radical R 3 O is selected from 4-phenylphenoxy, 2-phenylphenoxy, 2,6-diphenylphenoxy, 2,4,6-triphenylphenoxy, 2,3,5,6-tetraphenylphenoxy, 2-(tert-butyl)-6-phenylphenoxy, 2,4-di(tert-butyl)-6-phenylphenoxy, 2,6-diisopropylphenoxy, 2,6-dimethylphenoxy, 2,6-di(tert-butyl)phenoxy, 4-methyl-2,6-di(tert-butyl)phenoxy, 2,6-dichloro-4-(tert-butyl)phenoxy, and 2,6-dibromo-4-(tert-butyl)phenoxy. The two aryloxy radicals can be carried by the same molecule, such as biphenyloxy radical, dinaphthoxy, or 1,8-naphthyldioxy. Preferably, the aryloxy radical R... 3 O is 2,6-diphenylphenoxy, 2-(tert-butyl)-6-phenylphenoxy, or 2,4-di(tert-butyl)-6-phenylphenoxy.

[0137] solvent

[0138] In another embodiment of the invention, the catalytic system may optionally include one or more solvents.

[0139] In one embodiment, a solvent or a mixture of solvents may be used during the oligomerization reaction.

[0140] One or more solvents are advantageously selected from ethers, alcohols, halogenated solvents and hydrocarbons, which may be saturated or unsaturated, cyclic or acyclic, aromatic or non-aromatic, comprising 1 to 20 carbon atoms, preferably 4 to 15 carbon atoms, more preferably 4 to 12 carbon atoms and even more preferably 4 to 8 carbon atoms.

[0141] Preferably, the solvent is selected from pentane, hexane, cyclohexane, methylcyclohexane, heptane, butane or isobutane, 1,5-cyclooctadiene, benzene, toluene, o-xylene, mesitylene, ethylbenzene, diethyl ether, tetrahydrofuran, 1,4-dioxane, dichloromethane, dichloroethane, tetrachloroethane, hexachloroethane, chlorobenzene, dichlorobenzene, butene, hexene, and octene, either pure or as a mixture.

[0142] Preferably, the solvent can be advantageously selected from the product of the oligomerization reaction. Preferably, the solvent used is cyclohexane.

[0143] Preferably, when a solvent is used in the oligomerization process, the mass content of the solvent introduced into the reactor used in the process according to the invention is between 0.2 and 10.0, preferably between 0.5 and 5.0, and most preferably between 1.0 and 4.0. The solvent content is the mass ratio of the total flow rate of the solvent injected in the process to the total flow rate of the injected gaseous ethylene.

[0144] Preferably, the obtained linear α-olefin comprises 4 to 20 carbon atoms, more preferably 4 to 18 carbon atoms, more preferably 4 to 10 carbon atoms, and more preferably 4 to 8 carbon atoms. Preferably, the olefin is a linear α-olefin selected from 1-butene, 1-hexene, and 1-octene.

[0145] Advantageously, the oligomerization process is carried out at a pressure between 0.1 and 10.0 MPa, preferably between 0.2 and 9.0 MPa and more preferably between 0.3 and 8.0 MPa, at a temperature between 30 and 200°C, preferably between 35 and 150°C and more preferably between 45 and 140°C.

[0146] Preferably, the concentration of the catalyst in the catalytic system is between 0.001 and 300.0 ppm relative to the reaction mass, based on the mass of atomic metals, preferably between 0.002 and 100.0 ppm relative to the reaction mass, preferably between 0.003 and 50.0 ppm, more preferably between 0.05 and 20.0 ppm, and even more preferably between 0.1 and 10.0 ppm.

[0147] According to one embodiment, the oligomerization process is carried out in batches. The catalytic system configured as described above is introduced into a reactor according to the invention, advantageously equipped with heating and cooling devices. Pressurization is then carried out to the desired pressure using ethylene, and the temperature is adjusted to the desired value. The pressure in the reactor is kept constant by introducing gaseous olefin feedstock until the total volume of the produced liquid is, for example, 1 to 1000 times the volume of the pre-introduced catalytic solution. The catalyst is then destroyed by any commonly known method of the art, and the reaction products and solvent are then extracted and separated.

[0148] According to another embodiment, the oligomerization process is carried out continuously. The catalytic system configured as described above is simultaneously injected into the reactor according to the invention along with a gaseous olefin feedstock (preferably ethylene) and maintained at a desired temperature. Components of the catalytic system can also be injected separately into the reaction medium. The gaseous olefin feedstock (preferably gaseous ethylene) is introduced via a pressure-controlled inlet valve, which keeps the pressure constant in the reactor. The reaction mixture is pumped out by means of a level control valve to maintain the level constant. The catalyst is continuously destroyed by any common method known to those skilled in the art, and the products generated by the reaction, along with the solvent, are then separated, for example, by distillation. Unconverted ethylene can be recovered into the reactor. Catalyst residues, including those in the heavy fraction, can be incinerated.

[0149] Example

[0150] The following examples illustrate the invention, but do not limit its scope.

[0151] Example 1 (Comparison):

[0152] The ethylene oligomerization process was carried out in a bubble column reactor. The reactor operated at a pressure of 5.0 MPa and a temperature of 120°C. According to... Figure 1 The reaction volume consists of two zones, A and B, a tower with a diameter of 2.97 m and a liquid height of 6.0 m, and a total volume of 5.0 m³. 3 It consists of a recirculation loop.

[0153] The tower is equipped with a device for injecting gaseous ethylene, which is located 1.0m from the bottom of the tower.

[0154] As described in patent FR 3 019 064, in the presence of cyclohexane as a solvent, the catalytic system introduced into the reaction chamber is a chromium-based catalytic system with a chromium content of 5.2 ppm.

[0155] The purging flow rate is 0.0045 kg / s.

[0156] The reactor has a unit volume productivity of 0.13 tons of 1-hexene per hour, per cubic meter of reaction volume.

[0157] This reactor achieves a performance level that allows for 52.6% saturation of dissolved ethylene.

[0158] With a solvent mass ratio of 1.0, the yield of 1-hexene is 6.25 tons / hour, the selectivity for 1-hexene is 80.5 wt%, and the residence time in the reactor is 78.5 minutes. The solvent mass ratio is calculated as the mass ratio of the flow rate of the injected solvent to the flow rate of the injected gaseous ethylene.

[0159] Example 2 (according to the present invention):

[0160] Ethylene oligomerization was carried out in a bubble column gas / liquid reactor. The reactor operated at a pressure of 5.0 MPa and a temperature of 120 °C. According to... Figure 2 The reaction volume consists of two zones, A and B, a tower with a diameter of 2.97 m and a liquid height of 6.0 m, and a total volume of 5.0 m³. 3 It consists of a recirculation loop.

[0161] According to the invention, the tower is equipped with a gaseous ethylene injection device and a liquid product injection device, which allows the initial size of the ethylene bubbles to be reduced to one-fifth. These dispensers are located 1.0 m from the bottom of the tower.

[0162] As described in patent FR 3 019 064, in the presence of cyclohexane as a solvent, the catalytic system introduced into the reaction chamber is a chromium-based catalytic system with a chromium content of 3.0 ppm.

[0163] The purging flow rate is 0.0045 kg / s.

[0164] The reactor's productivity per unit volume is the same as in the previous example.

[0165] This reactor achieves a performance level that allows for 90.5% saturation of dissolved ethylene.

[0166] With a solvent mass ratio of 1.0, the yield of 1-hexene is 6.25 tons / hour, the selectivity for 1-hexene is 83.3 wt%, and the residence time in the reactor is 69.8 minutes. The solvent ratio is calculated as the mass ratio of the flow rate of the injected solvent to the flow rate of the injected gaseous ethylene.

[0167] Therefore, compared to the prior art, the apparatus according to the invention enables an increase in ethylene saturation by 37.9%, and thus an increase in selectivity for α-olefins by 2.8%, while reducing catalyst consumption (catalyst concentration of 72%), and thus reducing the operating cost of the process.

Claims

1. A process for oligomerizing gaseous olefin feedstock, comprising contacting a liquid comprising a catalytic system with the gaseous olefin feedstock by means of a gas injection device and a liquid injection device, said catalytic system comprising a metal catalyst, at least one activator and at least one additive, said injection device being arranged such that the injection of liquid causes a reduction in the size of gaseous ethylene bubbles by shearing, said process using a gas / liquid reactor for oligomerizing gaseous olefin feedstock, said gas / liquid reactor comprising a gas injection device (3), a liquid injection device (12) and a reaction chamber, said gas injection device comprising at least one gas injection orifice, said reaction chamber having an elongated shape along a vertical axis ... The reaction chamber includes a liquid phase in a lower region and a gas phase in an upper region above the lower region. The lower region of the reaction chamber includes an upper portion and a lower portion. A liquid injection device and a gas injection device are arranged together in the lower portion of the reaction chamber. The liquid injection device includes at least one liquid injection orifice. Each gas injection orifice is located near the orifice of the liquid injection device (12) and is positioned such that the gas injection trajectory is in the plane of the liquid injection trajectory. The injection device is arranged such that the liquid injection can reduce the bubble size by shearing during the injection of the gaseous olefin feedstock.

2. The process according to claim 1, wherein, The liquid injection orifice and the gas injection orifice are circular, and the diameter of the liquid injection orifice is greater than or equal to the diameter of the gas injection orifice.

3. The process according to claim 1, wherein, At least one gas injection orifice and at least one liquid injection orifice are positioned so that they face each other at an angle between 0° and 180°.

4. The process according to any one of claims 1-3, wherein, The gas injection device and the liquid injection device are selected from pipes, pipe meshes, multi-pipe distributors, perforated plates, cylindrical pipes, and concentric pipes.

5. The process according to claim 4, wherein, The gas injection device is a cylindrical tube in the form of an annular ring with injection orifices, and the liquid injection device is a cylindrical tube in the form of an annular ring with injection orifices.

6. The process according to claim 5, wherein, The diameter of the annular gas injection device is smaller than the diameter of the annular liquid injection device, and the gas injection device is positioned inside the liquid injection device on different planes.

7. The process according to claim 6, wherein, A series of liquid and gas injection devices, arranged in a ring with decreasing diameter, alternate from the periphery to the center, represented by the central axis of the device with the largest diameter. The devices are positioned such that the gas injection orifice of the gas injection device is positioned close to the orifice of the adjacent liquid injection device, such that the liquid injection trajectory and the gas injection trajectory are in the same plane, thereby causing shearing of the gas.

8. The process according to any one of claims 1-3, wherein, The orifices of the gas injection device and the liquid injection device each extend through pipes (13, 15).

9. The process according to claim 8, wherein, The diameter of the tube (13) of the gas injection device (3) is smaller than the diameter of the tube (15) of the liquid injection device (12), and the opening outlet end of the tube (13) of the gas injection device (3) is coaxially positioned inside the liquid injection tube.

10. The process according to any one of claims 1-3, wherein, The liquid injection pipe (15) includes a deflector.

11. The process according to any one of claims 1-3, wherein, The liquid injection pipe (15) has a tapered section at its end with a tapered outlet diameter.

12. The process according to any one of claims 1-3, wherein: The liquid phase includes reaction products, dissolved and gaseous olefin feedstocks, a catalytic system, and a solvent. The gas phase includes gaseous olefin feedstock and non-condensable gases. The process includes: - A device for introducing the catalytic system, the device being located in the lower portion of the reaction chamber. - A recirculation loop comprising an extraction device at the base of the reaction chamber for extracting a portion of the liquid, a heat exchanger for cooling the liquid, and a device for introducing the cooled liquid, the introduction device being located in the upper portion of the lower region of the reaction chamber. - and a gas phase recovery loop for recovering at least a portion of the gas phase to the lower region of the liquid phase, the gas phase recovery loop including an extraction device located in the upper region of the reaction chamber to extract a gas portion of the gas phase and an introduction device located in the lower region of the reaction chamber to introduce the extracted gas portion into the liquid phase.

13. The process according to any one of claims 1-3, wherein, The gaseous olefin feedstock comprises 2 to 6 carbon atoms.

14. The process according to any one of claims 1-3, wherein, The injection velocity of the liquid is greater than the injection velocity of the gaseous olefin feedstock, thereby promoting the shearing of the olefin bubbles into smaller bubbles.

15. The process according to claim 12, wherein, Ethane is a non-condensable gas.

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