EP1434650A1 - Reactor for oxidizing reaction of a liquid with a gas - Google Patents

Reactor for oxidizing reaction of a liquid with a gas

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Publication number
EP1434650A1
EP1434650A1 EP02795302A EP02795302A EP1434650A1 EP 1434650 A1 EP1434650 A1 EP 1434650A1 EP 02795302 A EP02795302 A EP 02795302A EP 02795302 A EP02795302 A EP 02795302A EP 1434650 A1 EP1434650 A1 EP 1434650A1
Authority
EP
European Patent Office
Prior art keywords
reactor
plates
orifices
gas
oxidation
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Withdrawn
Application number
EP02795302A
Other languages
German (de)
French (fr)
Inventor
François SEIDLITZ
Corinne Mathieu
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
Rhodia Polyamide Intermediates SAS
Original Assignee
Rhodia Polyamide Intermediates SAS
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Rhodia Polyamide Intermediates SAS filed Critical Rhodia Polyamide Intermediates SAS
Publication of EP1434650A1 publication Critical patent/EP1434650A1/en
Withdrawn legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C409/00—Peroxy compounds
    • C07C409/02—Peroxy compounds the —O—O— group being bound between a carbon atom, not further substituted by oxygen atoms, and hydrogen, i.e. hydroperoxides
    • C07C409/14—Peroxy compounds the —O—O— group being bound between a carbon atom, not further substituted by oxygen atoms, and hydrogen, i.e. hydroperoxides the carbon atom belonging to a ring other than a six-membered aromatic ring
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J10/00—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J10/00—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor
    • B01J10/002—Chemical processes in general for reacting liquid with gaseous media other than in the presence of solid particles, or apparatus specially adapted therefor carried out in foam, aerosol or bubbles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/0053—Details of the reactor
    • B01J19/006—Baffles
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J19/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J19/24—Stationary reactors without moving elements inside
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C29/00—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring
    • C07C29/48—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups
    • C07C29/50—Preparation of compounds having hydroxy or O-metal groups bound to a carbon atom not belonging to a six-membered aromatic ring by oxidation reactions with formation of hydroxy groups with molecular oxygen only
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C407/00—Preparation of peroxy compounds
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C45/00—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds
    • C07C45/27—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation
    • C07C45/32—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen
    • C07C45/33—Preparation of compounds having >C = O groups bound only to carbon or hydrogen atoms; Preparation of chelates of such compounds by oxidation with molecular oxygen of CHx-moieties
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C51/00—Preparation of carboxylic acids or their salts, halides or anhydrides
    • C07C51/16—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation
    • C07C51/31—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting
    • C07C51/313—Preparation of carboxylic acids or their salts, halides or anhydrides by oxidation of cyclic compounds with ring-splitting with molecular oxygen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00164—Controlling or regulating processes controlling the flow
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00761—Details of the reactor
    • B01J2219/00763—Baffles
    • B01J2219/00765—Baffles attached to the reactor wall
    • B01J2219/00777—Baffles attached to the reactor wall horizontal
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/18—Details relating to the spatial orientation of the reactor
    • B01J2219/185—Details relating to the spatial orientation of the reactor vertical
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/19—Details relating to the geometry of the reactor
    • B01J2219/194—Details relating to the geometry of the reactor round
    • B01J2219/1941—Details relating to the geometry of the reactor round circular or disk-shaped
    • B01J2219/1943—Details relating to the geometry of the reactor round circular or disk-shaped cylindrical
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
    • C07C2601/00—Systems containing only non-condensed rings
    • C07C2601/12—Systems containing only non-condensed rings with a six-membered ring
    • C07C2601/14—The ring being saturated

Definitions

  • the invention relates to a reactor suitable for an oxidation reaction of a liquid with an oxygen-containing gas.
  • Such a reactor can be used, for example, for the oxidation of cyclohexane during the preparation of intermediate products of adipic acid, such as cyclohexyl hydroperoxide, cyclohexanol or cyclohexanone.
  • Oxidation of liquid cyclohexane with oxygen in the air produces a mixture of cyclohexyl hydroperoxide (HPOCH), cyclohexanol (OL), cyclohexanone (ONE) and by-products called "heavy".
  • HPOCH cyclohexyl hydroperoxide
  • OL cyclohexanol
  • ONE cyclohexanone
  • FIG. 1 represents, for a reaction of this type, the evolution of the concentrations of desired product (C ⁇ and of by-products (C 2 ) as a function of time.
  • the above-mentioned reaction is interrupted in advance, at an instant t. There then remains a significant proportion of the compound to be oxidized which is made to recirculate in order to subject it to a new oxidation reaction.
  • a reactor of the “piston-reactor” type that is to say in a reactor which can be modeled as an enclosure in which moves a “slice” of reaction medium whose concentration in different products varies according to its position in the reactor, rather than in a “stirred” reactor in which the concentrations in the reaction medium are in all points equal to the output concentrations.
  • the concentration of product is important only near the outlet of the reactor.
  • the formation of unwanted by-products, which increases with the concentration of product is significant only in the terminal part of the reactor.
  • the reaction is carried out in reactors, called “bubble columns”, into which the oxidizing gas is injected at the bottom, that is to say at the bottom, into the reaction medium. From a certain diameter, it is known that these bubble columns can be considered as reactors stirred with regard to the reaction medium.
  • Such a stepped supply must therefore be provided with an elaborate control system, which significantly increases its cost. Furthermore, such a staged supply is bulky and difficult to use industrially. In addition, it requires the installation of complex piping.
  • the invention goes against the habits of the technical field considered by avoiding the use of a stepped oxygen supply in a reactor divided into stages but without giving up an effective and necessary securing of the installation.
  • the invention relates to a reactor for an oxidation reaction of a liquid with an oxygen-containing gas, this reactor being supplied solely at the bottom with a compound to be oxidized and an oxidizing gas.
  • This reactor is characterized in that it is divided into stages by separating plates provided with passage orifices compatible only with a unidirectional flow of the reaction medium and capable of preventing an accumulation of gas under each of the plates.
  • a single supply of oxidizing gas is provided, which opens at the bottom of the reactor, this supply making it possible to deliver the oxygen which will be consumed in the different stages of the reactor.
  • the oxidizing gas must therefore be able to circulate between these different stages, as must the reaction medium, for example cyclohexane.
  • this mixture can accumulate under certain trays by forming a gaseous mat, in particular during the voluntary or involuntary interruption of the supply of oxidizing gas.
  • the passage orifices provided in this tray make it possible to eliminate any risk of the formation of a gas blanket because the bubbles are evacuated through the abovementioned passage orifices.
  • passage openings of the plates also make it possible to channel the two-phase flow inside the reactor, in a single direction, from bottom to top, which reduces its axial dispersion and makes it possible to create a “piston” type reactor flow. Finally, these passage openings make it possible to limit the pressure losses induced by the plates.
  • the above-mentioned reactor incorporates one or more of the following characteristics: -
  • the orifices of the plates have a section equivalent to a circular section with a diameter between 10 and 100 mm, preferably between 15 and 50 mm.
  • the trays have an opening rate of between 10 and 50% preferably, between 10 and 30%. This opening rate is the percentage of the surface of a tray corresponding to the orifices relative to the total surface of the tray.
  • the orifices are substantially evenly distributed on the plates. In this case, they can be distributed with a mesh with a triangular, rectangular or hexagonal base.
  • the invention also relates to the use of a reactor as previously described for the oxidation of hydrocarbons into different products such as hydroperoxide, ketone, alcohol and / or acid.
  • this reactor is used for the oxidation of cyclohexane, with oxygen or air, to cyclohexyl hydroperoxide, cyclohexanone, cyclohexanol and / or adipic acid.
  • Other uses of such a reactor can be provided, for example for the oxidation of cumene to phenol.
  • FIG. 2 is a schematic representation of a principle of part of an oxidation installation incorporating a reactor according to the invention
  • FIG. 3 is a section along line III-III in Figure 2;
  • FIG. 4 is a principle representation of the evolution of the pressure difference between two levels in the reactor of Figure 1, under certain conditions of use;
  • FIG. 5 is a partial view in principle of the plate shown in Figure 3;
  • FIG. 6 is a view similar to FIG. 5, for a reactor according to a second embodiment of the invention and
  • FIG. 7 is a view according to Figure 5, for a reactor according to a third embodiment of the invention.
  • the reactor 1 shown in the figures comprises a tank 2 into which opens a conduit 3 for supplying the compound to be oxidized, for example cyclohexane, from a source not shown.
  • a pump 4 is inserted in the conduit 3 in order to convey the cyclohexane in the tank 2 with a controlled flow.
  • a second conduit 3 ' is provided in the upper part of the tank 3 to evacuate the reaction medium.
  • a system for supplying oxidizing gas to the reactor 1 is provided and comprises a duct 5 connected to a source 6 of pressurized air.
  • oxidizing gas is meant oxygen or an oxygen-containing gas, such as air or oxygen-enriched air.
  • the conduit 5 opens at the foot of the tank 2, that is to say at the bottom of the latter, and is connected to a pipe 8 in the form of a serpentine centered on a substantially vertical central axis ZZ 'of the tank 2 and provided with air passage holes.
  • several pipes in the form of rings centered on the axis ZZ ′ could be used.
  • a pipe 9 is provided at the top of the tank 2 to evacuate the gas phase consisting of gas from the oxidizing gas and vapors.
  • the arrow Ei represents the flow of cyclohexane in the lower part, or foot, 2a of the tank 2.
  • the arrows E 2 represent the flow of oxidizing gas in this part.
  • the reactor 1 is divided into stages by plates 10 kept at a distance from each other by means of rods-spacers 11. Other means of fixing the plates 10 in the tank 2 can be used.
  • Each plate 10 is provided with orifices 12 for passage of the reaction medium and of the oxidizing gas originating respectively from the pipe 3 and the pipe 8.
  • the reactor can thus be divided into several stages 14 each constituting a unitary reactor.
  • Reactor 1 must be secured against malfunctions in its supply systems. For example, it must make it possible to avoid or limit as much as possible the risks of gas self-ignition. Under the conditions of operating temperature and pressure, steam cyclohexane is created, the mixture of cyclohexane vapors and oxygen being able to form an explosive mixture without source of ignition. It is therefore advisable to avoid as much as possible the accumulation of such a gaseous mixture under the plates. In addition, the pressure losses induced by the plates 10 must be as low as possible for the reasons indicated above. In view of the above, it is advantageous for the orifices 12 to be as large as possible.
  • the orifices 12 must not be too wide in order to give the flow E of the two-phase mixture in the tank 2 an upward direction, without significant return of liquid from an upper stage 14 to a lower stage.
  • disengagement time ⁇ t which corresponds to the time of evacuation of gas between two predetermined levels of the reactor after interruption of the supply of oxidizing gas.
  • differential pressure sensor 15 installed to measure the pressure difference on either side of a plate 10.
  • the sensor 15 is connected by two tapping lines 15a and 15b to two successive stages 14 of the reactor 1.
  • the sensor 15 can also measure the difference across several plates 10, in which case it is connected to non-successive stages.
  • a second differential pressure sensor 16 is connected by tapping lines 16a and 16b at two points of different heights relative to the bottom of the tank 2, within the same stage 14.
  • the sensor 15 makes it possible to measure the pressure drops through a plate 10 and the time of disengagement of the gas through this plate.
  • the sensor 16 makes it possible to measure the gas retention in a stage 14. If one stops, at an instant t 0 / the supply of cyclohexane and of oxidizing gas to the reactor 1, the pressure difference ⁇ P ⁇ 6 measured by the sensor 16 decreases, as shown in FIG. 4 by the curve ⁇ P ⁇ 6 . Under the same conditions, the pressure difference ⁇ P ⁇ 5 measured by the sensor 15 increases by a value ⁇ and then decreases.
  • ⁇ t the time interval between instant t 0 and instant ti where ⁇ P 15 reaches its lower plateau value. Between instants to and ti, there is a transient phase of disengagement of the gas present in the reactor 1.
  • the diameter d ⁇ 2 greater than 10 mm is chosen to prevent any possible fouling of the orifices 12 leading to significant blockage of some or all of these orifices.
  • the diameter d ⁇ 2 is chosen to be less than 100 mm so that the flow in the orifices 12 remains unidirectional in the direction of the arrows El and E2 in FIG. 2, that is to say substantially vertical and directed upwards.
  • the diameter d 12 is chosen between 15 and 50 mm, the disengagement time then being, surprisingly, substantially equivalent to that of a reactor devoid of a tray.
  • the plates 10 of the reactor 1 according to the invention do not disturb the free evacuation of the gas.
  • D 2 denotes the diameter of the tank 2.
  • the A ⁇ area 0 of a tray 10 is equal to ⁇ D 2 2/4.
  • the area of an orifice 12 is equal to ⁇ d ⁇ 2 2/4.
  • N the number of orifices 12 of a tray 10.
  • N is chosen so that this opening rate V is between 10 and 50%, preferably between 10 and 30%.
  • V is between 10 and 50%, preferably between 10 and 30%.
  • the essentially unidirectional and ascending nature of the flow E can be verified by the technique known as “measurement of distribution of residence times” carried out by injection of a tracer.
  • the orifices 12 can be equi-distributed with a substantially triangular mesh. They can also be equally distributed with a substantially square mesh, as shown in FIG. 6, or with a mesh with a substantially hexagonal base, as represented in FIG. 7. Other geometric distributions of the orifices 12 in the plates 10 can be considered.
  • the orifices 12 are not necessarily of circular section, even if such a section is preferred for the reason of ease of production of the plates 10.
  • the plates 10 can be produced by plates of sufficient thickness to obtain resistance suitable mechanical, the orifices 12 being obtained by knocking out in the case of metal plates.
  • the plates can be metallic, ceramic or made of any other material suited to their conditions of use.
  • the invention has been described with reference to an oxidation reaction of cyclohexane. However, it is not limited to this reaction and a reactor according to the invention can be used in any reaction for the oxidation of a liquid by means of a gas containing oxygen and, in particular, for the oxidation of a hydrocarbon, for example the transformation of cumene into phenol.

Abstract

The invention concerns a reactor (1) for oxidizing reaction of a liquid with a gas containing oxygen divided into stages (14) by separating plates (10). The means (5-8) feeding the reactor (1) with compound to be oxidized (E1) and oxidizing gas (E2) emerge solely at the base (2a) of the reactor (1), whereas the plates (10) are provided with passage holes (12) solely compatible with a unidirectional flow (E) of the reaction medium and designed to prevent gas accumulation beneath each of the plates (10).

Description

Réacteur pour réaction d'oxydation d'un liquide avec un gaz Reactor for oxidation reaction of a liquid with a gas
L'invention a trait à un réacteur adapté pour une réaction d'oxydation d'un liquide avec un gaz contenant de l'oxygène.The invention relates to a reactor suitable for an oxidation reaction of a liquid with an oxygen-containing gas.
Un tel réacteur peut être employé, par exemple, pour l'oxydation de cyclohexane lors de la préparation de produits intermédiaires de l'acide adipique, tels que l'hydropéroxyde de cyclohexyle, le cyclohexanol ou la cyclohexanone.Such a reactor can be used, for example, for the oxidation of cyclohexane during the preparation of intermediate products of adipic acid, such as cyclohexyl hydroperoxide, cyclohexanol or cyclohexanone.
L'oxydation de cyclohexane liquide avec l'oxygène de l'air produit un mélange d'hydropéroxyde de cyclohexyle (HPOCH), de cyclohexanol (OL), de cyclohexanone (ONE) et de sous-produits, dits « lourds ».Oxidation of liquid cyclohexane with oxygen in the air produces a mixture of cyclohexyl hydroperoxide (HPOCH), cyclohexanol (OL), cyclohexanone (ONE) and by-products called "heavy".
Dans cette réaction d'oxydation mettant en œuvre un mécanisme radicalaire en chaîne, le taux de transformation du composé à oxyder, en fonction du temps est maintenu à une valeur faible pour éviter la formation de sous-produits ou de produits non désirés. La figure 1 représente, pour une réaction de ce type, l'évolution des concentrations en produit désiré (C^ et en sous-produits (C2) en fonction du temps. Pour éviter une dégradation trop importante du produit désiré en sous-produits, on interrompt la réaction précitée de façon anticipée, à un instant t,. Il reste alors une proportion importante du composé à oxyder que l'on fait recirculer pour le soumettre à une nouvelle réaction d'oxydation.In this oxidation reaction using a radical chain mechanism, the transformation rate of the compound to be oxidized, as a function of time, is kept at a low value to avoid the formation of by-products or unwanted products. FIG. 1 represents, for a reaction of this type, the evolution of the concentrations of desired product (C ^ and of by-products (C 2 ) as a function of time. To avoid excessive degradation of the desired product into by-products , the above-mentioned reaction is interrupted in advance, at an instant t. There then remains a significant proportion of the compound to be oxidized which is made to recirculate in order to subject it to a new oxidation reaction.
Pour améliorer la sélectivité en produit désiré de la réaction précitée, on sait qu'il est préférable de travailler dans un réacteur de type « réacteur-piston », c'est-à-dire dans un réacteur qui peut être modélisé comme une enceinte dans laquelle se déplace une « tranche » de milieu réactionnel dont la concentration en différents produits varie en fonction de sa position dans le réacteur, plutôt que dans un réacteur « agité » dans lequel les concentrations dans le milieu réactionnel sont en tous points égales aux concentrations de sortie. Dans le cas du réacteur « piston », la concentration en produit n'est importante qu'à proximité de la sortie du réacteur. Ainsi, la formation de sous-produits non désirés, qui croit avec la concentration en produit, n'est significative que dans la partie terminale du réacteur.To improve the selectivity of the aforementioned reaction to the desired product, it is known that it is preferable to work in a reactor of the “piston-reactor” type, that is to say in a reactor which can be modeled as an enclosure in which moves a “slice” of reaction medium whose concentration in different products varies according to its position in the reactor, rather than in a “stirred” reactor in which the concentrations in the reaction medium are in all points equal to the output concentrations. In the case of the "piston" reactor, the concentration of product is important only near the outlet of the reactor. Thus, the formation of unwanted by-products, which increases with the concentration of product, is significant only in the terminal part of the reactor.
Dans les installations connues, on réalise la réaction dans des réacteurs, dits « colonnes à bulles », dans lesquels le gaz oxydant est injecté en pied, c'est-à-dire en partie basse, dans le milieu réactionnel. A partir d'un certain diamètre, il est connu que ces colonnes à bulles peuvent être considérées comme des réacteurs agités au regard du milieu réactionnel.In known installations, the reaction is carried out in reactors, called “bubble columns”, into which the oxidizing gas is injected at the bottom, that is to say at the bottom, into the reaction medium. From a certain diameter, it is known that these bubble columns can be considered as reactors stirred with regard to the reaction medium.
Pour améliorer la similitude avec un réacteur « piston », on peut envisager de diviser le réacteur en plusieurs réacteurs unitaires grâce à des cloisons séparatrices internes évitant la recirculation du milieu réactionnel. Dans ce cas, il est connu, par exemple de EP- A-0 135 718 ou de US-A-3, 530, 185, de prévoir des arrivées réparties d'oxygène pour procéder à une oxydation dans chaque réacteur unitaire. La quantité d'oxygène introduite dans chaque réacteur unitaire doit être contrôlée de façon précise pour que la quasi-totalité de l'oxygène injecté soit consommée. Ceci vise à éviter, pour des raisons de sécurité, la présence d'un matelas gazeux, riche en vapeurs du composé à oxyder et en oxygène, en dessous d'une ou plusieurs cloisons intermédiaires du réacteur. En effet, ces vapeurs et l'oxygène pourraient former un mélange explosif dans certaines conditions d'exploitation. Une telle alimentation étagée doit donc être munie d'un système de contrôle élaboré, ce qui majore sensiblement son coût. Par ailleurs, une telle alimentation étagée est encombrante et délicate à exploiter industriellement. En outre, elle nécessite la pose de tuyauteries complexes. L' invention prend le contre-pied des habitudes du domaine technique considéré en évitant l'utilisation d'une alimentation étagée en oxygène dans un réacteur divisé en étages mais sans renoncer à une sécurisation efficace et nécessaire de l'installation.To improve the similarity with a “piston” reactor, it is possible to consider dividing the reactor into several unit reactors by means of internal separating partitions avoiding recirculation of the reaction medium. In this case, it is known, for example from EP-A-0 135 718 or from US-A-3, 530, 185, to provide distributed oxygen inlets to carry out oxidation in each unit reactor. The quantity of oxygen introduced into each unit reactor must be precisely controlled so that almost all of the injected oxygen is consumed. This is to avoid, for safety reasons, the presence of a gas blanket, rich in vapors of the compound to be oxidized and in oxygen, below one or more intermediate partitions of the reactor. Indeed, these vapors and oxygen could form an explosive mixture under certain operating conditions. Such a stepped supply must therefore be provided with an elaborate control system, which significantly increases its cost. Furthermore, such a staged supply is bulky and difficult to use industrially. In addition, it requires the installation of complex piping. The invention goes against the habits of the technical field considered by avoiding the use of a stepped oxygen supply in a reactor divided into stages but without giving up an effective and necessary securing of the installation.
Dans cet esprit, l'invention concerne un réacteur pour une réaction d'oxydation d'un liquide avec un gaz contenant de l'oxygène, ce réacteur étant alimenté uniquement en pied avec un composé à oxyder et un gaz oxydant. Ce réacteur est caractérisé en ce qu'il est divisé en étages par des plateaux séparateurs munis d'orifices de passage compatibles uniquement avec un écoulement unidirectionnel du milieu réactionnel et aptes à empêcher une accumulation de gaz sous chacun des plateaux. Dans un réacteur conforme à l'invention, une unique alimentation en gaz oxydant est prévue, qui débouche en partie inférieure du réacteur, cette alimentation permettant de délivrer l'oxygène qui sera consommé dans les différents étages du réacteur. Le gaz oxydant doit donc pouvoir circuler entre ces différents étages, de même que le milieu réactionnel, par exemple du cyclohexane. Or, compte tenu des températures et des pressions régnant dans un réacteur industriel d'oxydation, on pourrait être confronté à un risque d'auto-inflammation d'un mélange gazeux formé par le gaz oxydant et les vapeurs du composé à oxyder, ce mélange pouvant s'accumuler sous certains plateaux en formant un matelas gazeux, notamment lors de l'interruption volontaire ou involontaire de l'alimentation en gaz oxydant. Grâce à l'invention, les orifices de passage prévus dans ce plateau permettent d'éliminer tout risque de formation d'un matelas de gaz car les bulles sont évacuées à travers les orifices de passage précités. Les orifices de passage des plateaux permettent également de canaliser l'écoulement diphasique à l'intérieur du réacteur, selon une seule direction, de bas en haut, ce qui réduit sa dispersion axiale et permet de créer un écoulement de type réacteur « piston ». Enfin, ces orifices de passages permettent de limiter les pertes de charges induites par les plateaux.In this spirit, the invention relates to a reactor for an oxidation reaction of a liquid with an oxygen-containing gas, this reactor being supplied solely at the bottom with a compound to be oxidized and an oxidizing gas. This reactor is characterized in that it is divided into stages by separating plates provided with passage orifices compatible only with a unidirectional flow of the reaction medium and capable of preventing an accumulation of gas under each of the plates. In a reactor according to the invention, a single supply of oxidizing gas is provided, which opens at the bottom of the reactor, this supply making it possible to deliver the oxygen which will be consumed in the different stages of the reactor. The oxidizing gas must therefore be able to circulate between these different stages, as must the reaction medium, for example cyclohexane. However, given the temperatures and pressures prevailing in an industrial oxidation reactor, one could be faced with a risk of self-ignition of a gaseous mixture formed by the oxidizing gas and the vapors of the compound to be oxidized, this mixture can accumulate under certain trays by forming a gaseous mat, in particular during the voluntary or involuntary interruption of the supply of oxidizing gas. Thanks to the invention, the passage orifices provided in this tray make it possible to eliminate any risk of the formation of a gas blanket because the bubbles are evacuated through the abovementioned passage orifices. The passage openings of the plates also make it possible to channel the two-phase flow inside the reactor, in a single direction, from bottom to top, which reduces its axial dispersion and makes it possible to create a “piston” type reactor flow. Finally, these passage openings make it possible to limit the pressure losses induced by the plates.
Selon des aspects avantageux mais non obligatoires de l'invention, le réacteur précité incorpore une ou plusieurs caractéristiques suivantes : - Les orifices des plateaux ont une section équivalente à une section circulaire de diamètre compris entre 10 et 100 mm, de préférence entre 15 et 50 mm.According to advantageous but not compulsory aspects of the invention, the above-mentioned reactor incorporates one or more of the following characteristics: - The orifices of the plates have a section equivalent to a circular section with a diameter between 10 and 100 mm, preferably between 15 and 50 mm.
Les plateaux présentent un taux d'ouverture compris entre 10 et 50% de préférence, entre 10 et 30%. Ce taux d'ouverture est le pourcentage de la surface d'un plateau correspondant aux orifices par rapport à la surface totale du plateau.The trays have an opening rate of between 10 and 50% preferably, between 10 and 30%. This opening rate is the percentage of the surface of a tray corresponding to the orifices relative to the total surface of the tray.
Les orifices sont sensiblement équi-répartis sur les plateaux. Dans ce cas, ils peuvent être répartis avec une maille à base triangulaire, rectangulaire ou hexagonale .The orifices are substantially evenly distributed on the plates. In this case, they can be distributed with a mesh with a triangular, rectangular or hexagonal base.
L'invention concerne également l'utilisation d'un réacteur tel que précédemment décrit pour l'oxydation d'hydrocarbures en différents produits tels que hydroperoxyde, cétone, alcool et/ou acide.The invention also relates to the use of a reactor as previously described for the oxidation of hydrocarbons into different products such as hydroperoxide, ketone, alcohol and / or acid.
A titre d'application particulière, ce réacteur est utilisé pour l'oxydation de cyclohexane, par de l'oxygène ou de l'air, en hydroperoxyde de cyclohexyle, cyclohexanone, cyclohexanol et/ou acide adipique. On peut prévoir d'autres utilisations d'un tel réacteur, par exemple pour l'oxydation de cumène en phénol.As a specific application, this reactor is used for the oxidation of cyclohexane, with oxygen or air, to cyclohexyl hydroperoxide, cyclohexanone, cyclohexanol and / or adipic acid. Other uses of such a reactor can be provided, for example for the oxidation of cumene to phenol.
L'invention sera mieux comprise et d'autres avantages de celle-ci apparaîtront plus clairement à la lumière de la description qui va suivre de trois modes de réalisation d'un réacteur conforme à son principe, donnée uniquement à titre d'exemple et faite en référence aux dessins annexés dans lesquels :The invention will be better understood and other advantages thereof will appear more clearly in the light of the following description of three embodiments of a reactor conforming to its principle, given solely by way of example and made with reference to the appended drawings in which:
- la figure 2 est une représentation schématique de principe d'une partie d'une installation d'oxydation incorporant un réacteur conforme à l'invention ;- Figure 2 is a schematic representation of a principle of part of an oxidation installation incorporating a reactor according to the invention;
- la figure 3 est une coupe selon la ligne III- III à la figure 2 ;- Figure 3 is a section along line III-III in Figure 2;
- la figure 4 est une représentation de principe de l'évolution de l'écart de pression entre deux niveaux dans le réacteur de la figure 1, dans certaines conditions d'utilisation ;- Figure 4 is a principle representation of the evolution of the pressure difference between two levels in the reactor of Figure 1, under certain conditions of use;
- la figure 5 est une vue partielle de principe du plateau représenté à la figure 3 ; - la figure 6 est une vue analogue à la figure 5, pour un réacteur conforme à un second mode de réalisation de l'invention et- Figure 5 is a partial view in principle of the plate shown in Figure 3; FIG. 6 is a view similar to FIG. 5, for a reactor according to a second embodiment of the invention and
- la figure 7 est une vue conforme à la figure 5, pour un réacteur conforme à un troisième mode de réalisation de l'invention.- Figure 7 is a view according to Figure 5, for a reactor according to a third embodiment of the invention.
Le réacteur 1 représenté sur les figures comprend une cuve 2 dans laquelle débouche un conduit 3 d' alimentation en composé à oxyder, par exemple du cyclohexane, à partir d'une source non représentée. Une pompe 4 est insérée dans le conduit 3 afin d'acheminer le cyclohexane dans la cuve 2 avec un débit contrôlé .The reactor 1 shown in the figures comprises a tank 2 into which opens a conduit 3 for supplying the compound to be oxidized, for example cyclohexane, from a source not shown. A pump 4 is inserted in the conduit 3 in order to convey the cyclohexane in the tank 2 with a controlled flow.
Un second conduit 3' est prévu en partie supérieure de la cuve 3 pour évacuer le milieu réactionnel. Un système d'alimentation en gaz oxydant du réacteur 1 est prévu et comprend un conduit 5 relié à une source 6 d'air sous pression. Par gaz oxydant, on entend de l'oxygène ou un gaz contenant de l'oxygène, tel que de l'air ou de l'air enrichi en oxygène. Le conduit 5 débouche au pied de la cuve 2, c'est-à- dire en partie basse de celle-ci, et est relié à un tuyau 8 en forme de serpentin centré sur un axe central sensiblement vertical Z-Z' de la cuve 2 et pourvu d'orifices de passage d'air. En variante, plusieurs tuyaux en forme d'anneaux centrés sur l'axe Z-Z' pourraient être utilisés .A second conduit 3 'is provided in the upper part of the tank 3 to evacuate the reaction medium. A system for supplying oxidizing gas to the reactor 1 is provided and comprises a duct 5 connected to a source 6 of pressurized air. By oxidizing gas is meant oxygen or an oxygen-containing gas, such as air or oxygen-enriched air. The conduit 5 opens at the foot of the tank 2, that is to say at the bottom of the latter, and is connected to a pipe 8 in the form of a serpentine centered on a substantially vertical central axis ZZ 'of the tank 2 and provided with air passage holes. As a variant, several pipes in the form of rings centered on the axis ZZ ′ could be used.
Un tuyau 9 est prévu au sommet de la cuve 2 pour évacuer la phase gazeuse constituée de gaz provenant du gaz oxydant et de vapeurs.A pipe 9 is provided at the top of the tank 2 to evacuate the gas phase consisting of gas from the oxidizing gas and vapors.
On a représenté par la flèche Ei l'écoulement de cyclohexane dans la partie inférieure, ou pied, 2a de la cuve 2. On a représenté par les flèches E2 l'écoulement de gaz oxydant dans cette partie. Le réacteur 1 est divisé en étages par des plateaux 10 maintenus à distance les uns des autres au moyen de tiges- entretoises 11. D'autres moyens de fixation des plateaux 10 dans la cuve 2 peuvent être utilisés.The arrow Ei represents the flow of cyclohexane in the lower part, or foot, 2a of the tank 2. The arrows E 2 represent the flow of oxidizing gas in this part. The reactor 1 is divided into stages by plates 10 kept at a distance from each other by means of rods-spacers 11. Other means of fixing the plates 10 in the tank 2 can be used.
Chaque plateau 10 est pourvu d'orifices 12 de passage du milieu réactionnel et du gaz oxydant issus respectivement du conduit 3 et du tuyau 8.Each plate 10 is provided with orifices 12 for passage of the reaction medium and of the oxidizing gas originating respectively from the pipe 3 and the pipe 8.
Le réacteur peut ainsi être divisé en plusieurs étages 14 constituant chacun un réacteur unitaire.The reactor can thus be divided into several stages 14 each constituting a unitary reactor.
Le réacteur 1 doit être sécurisé contre les dysfonctionnements de ses systèmes d'alimentation. Par exemple, il doit permettre d'éviter ou de limiter au maximum les risques d'auto-inflammation de gaz. Dans les conditions de température et de pression d'exploitation, du cyclohexane vapeur est créé, le mélange de vapeurs de cyclohexane et d'oxygène pouvant former un mélange explosif sans source d'ignition. Il convient donc d'éviter au maximum l'accumulation d'un tel mélange gazeux sous les plateaux. En outre, les pertes de charge induites par les plateaux 10 doivent être aussi faibles que possible pour les raisons indiquées ci-dessus. Compte tenu de ce qui précède, on a intérêt à ce que les orifices 12 soient les plus grands possibles.Reactor 1 must be secured against malfunctions in its supply systems. For example, it must make it possible to avoid or limit as much as possible the risks of gas self-ignition. Under the conditions of operating temperature and pressure, steam cyclohexane is created, the mixture of cyclohexane vapors and oxygen being able to form an explosive mixture without source of ignition. It is therefore advisable to avoid as much as possible the accumulation of such a gaseous mixture under the plates. In addition, the pressure losses induced by the plates 10 must be as low as possible for the reasons indicated above. In view of the above, it is advantageous for the orifices 12 to be as large as possible.
Par ailleurs, les orifices 12 ne doivent pas être trop larges afin de conférer à l'écoulement E du mélange diphasique dans la cuve 2 une direction ascendante, sans retour notable de liquide d'un étage 14 supérieur vers un étage inférieur.Furthermore, the orifices 12 must not be too wide in order to give the flow E of the two-phase mixture in the tank 2 an upward direction, without significant return of liquid from an upper stage 14 to a lower stage.
Pour les raisons qui précèdent, les orifices 12 sont donc soumis à des contraintes de définition antinomiques.For the above reasons, the orifices 12 are therefore subject to conflicting definition constraints.
En ce qui concerne l'aspect de sécurité visant à éviter l'accumulation de gaz sous les plateaux 10, on peut définir la notion de temps de désengagement Δt qui correspond au temps d'évacuation du gaz entre deux niveaux prédéterminés du réacteur après interruption de l'alimentation en gaz oxydant.With regard to the safety aspect aiming to avoid the accumulation of gas under the plates 10, one can define the concept of disengagement time Δt which corresponds to the time of evacuation of gas between two predetermined levels of the reactor after interruption of the supply of oxidizing gas.
On considère un capteur 15 de pression différentielle installé pour mesurer l'écart de pression de part et d'autre d'un plateau 10. Le capteur 15 est relié par deux lignes de piquage 15a et 15b à deux étages 14 successifs du réacteur 1.We consider a differential pressure sensor 15 installed to measure the pressure difference on either side of a plate 10. The sensor 15 is connected by two tapping lines 15a and 15b to two successive stages 14 of the reactor 1.
Le capteur 15 peut également mesurer l'écart à travers plusieurs plateaux 10, auquel cas il est relié à des étages non successifs.The sensor 15 can also measure the difference across several plates 10, in which case it is connected to non-successive stages.
Par ailleurs, un second capteur de pression différentiel 16 est relié par des lignes de piquage 16a et 16b à deux points de hauteurs différentes par rapport au fond de la cuve 2, au sein d'un même étage 14.Furthermore, a second differential pressure sensor 16 is connected by tapping lines 16a and 16b at two points of different heights relative to the bottom of the tank 2, within the same stage 14.
Le capteur 15 permet de mesurer les pertes de charge à travers un plateau 10 et le temps de désengagement du gaz à travers ce plateau. Le capteur 16 permet de mesurer la rétention de gaz dans un étage 14. Si l'on arrête, à un instant t0/ l'alimentation en cyclohexane et en gaz oxydant du réacteur 1, l'écart de pression ΔPι6 mesuré par le capteur 16 décroît, comme représenté à la figure 4 par la courbe ΔPι6. Dans les mêmes conditions, l'écart de pression ΔPι5 mesuré par le capteur 15 augmente d'une valeur Δ puis décroît. On note Δt l'intervalle de temps entre l'instant t0 et l'instant ti où ΔP15 atteint sa valeur de palier inférieur. Entre les instants to et ti, il se produit une phase transitoire de désengagement du gaz présent dans le réacteur 1.The sensor 15 makes it possible to measure the pressure drops through a plate 10 and the time of disengagement of the gas through this plate. The sensor 16 makes it possible to measure the gas retention in a stage 14. If one stops, at an instant t 0 / the supply of cyclohexane and of oxidizing gas to the reactor 1, the pressure difference ΔPι 6 measured by the sensor 16 decreases, as shown in FIG. 4 by the curve ΔPι 6 . Under the same conditions, the pressure difference ΔPι 5 measured by the sensor 15 increases by a value Δ and then decreases. We denote by Δt the time interval between instant t 0 and instant ti where ΔP 15 reaches its lower plateau value. Between instants to and ti, there is a transient phase of disengagement of the gas present in the reactor 1.
En comparant des mesures faites dans un réacteur 1 muni de plateaux 10 comme représenté à la figure 2 et dans un réacteur dépourvu de plateau, on peut connaître le retard au désengagement du gaz engendré par le ou les plateaux, ce qui permet de comparer ce retard à la limite imposée par l'analyse de sécurité de l'installation.By comparing measurements made in a reactor 1 provided with plates 10 as shown in FIG. 2 and in a reactor without a plate, one can know the delay in the disengagement of the gas generated by the plate or plates, which makes it possible to compare this delay to the limit imposed by the safety analysis of the installation.
En pratique, en prenant des orifices 12 à section circulaire dont le diamètre dι2 est compris entre 10 et 100 mm, on obtient un temps de désengagement Δt inférieur à celui fixé par l'analyse de sécurité de l'installation.In practice, by taking orifices 12 of circular section whose diameter dι 2 is between 10 and 100 mm, one obtains a disengagement time Δt less than that fixed by the safety analysis of the installation.
On choisit le diamètre dι2 supérieur à 10 mm pour éviter qu'un encrassement éventuel des orifices 12 ne conduise à un bouchage significatif de certains ou de tous ces orifices. Le diamètre dι2 est choisit inférieur à 100 mm pour que l'écoulement dans les orifices 12 demeure unidirectionnel dans le sens des flèches El et E2 à la figure 2, c'est-à-dire sensiblement vertical et dirigé vers le haut.The diameter dι 2 greater than 10 mm is chosen to prevent any possible fouling of the orifices 12 leading to significant blockage of some or all of these orifices. The diameter dι 2 is chosen to be less than 100 mm so that the flow in the orifices 12 remains unidirectional in the direction of the arrows El and E2 in FIG. 2, that is to say substantially vertical and directed upwards.
De façon préférentielle, le diamètre d12 est choisi entre 15 et 50 mm, le temps de désengagement étant alors, de façon surprenante, sensiblement équivalent à celui d'un réacteur dépourvu de plateau. En d'autres termes, le ou les plateaux 10 du réacteur 1 conforme à l'invention ne perturbent pas la libre évacuation du gaz. On note D2 le diamètre de la cuve 2.Preferably, the diameter d 12 is chosen between 15 and 50 mm, the disengagement time then being, surprisingly, substantially equivalent to that of a reactor devoid of a tray. In other words, the plates 10 of the reactor 1 according to the invention do not disturb the free evacuation of the gas. D 2 denotes the diameter of the tank 2.
L'aire Aι0 d'un plateau 10 est égale à πD2 2 /4. L'aire d'un orifice 12 est égale à πdι2 2/4.The Aι area 0 of a tray 10 is equal to πD 2 2/4. The area of an orifice 12 is equal to πdι 2 2/4.
On note N le nombre d'orifices 12 d'un plateau 10. Le taux d'ouverture d'un plateau 10 est T = N x Aι2/Aι0 = N x dι2 2/d2 2.We denote by N the number of orifices 12 of a tray 10. The opening rate of a tray 10 is T = N x Aι 2 / Aι 0 = N x dι 2 2 / d 2 2 .
Compte tenu de la valeur des diamètres dι2 et D2, on choisit N de telle sorte que ce taux d'ouverture V soit compris entre 10 et 50%, de préférence entre 10 et 30%. Avec un tel taux d'ouverture, l'écoulement E est essentiellement unidirectionnel et ascendant dans la cuve 2, alors que, comme indiqué précédemment, les pertes de charge et le temps de désengagement demeurent compatibles avec un fonctionnement industriel sécurisé d'une installation incorporant un tel réacteur.Given the value of the diameters dι 2 and D 2 , N is chosen so that this opening rate V is between 10 and 50%, preferably between 10 and 30%. With such an opening rate, the flow E is essentially unidirectional and ascending in the tank 2, while, as indicated above, the pressure drops and the disengagement time remain compatible with secure industrial operation of an installation incorporating such a reactor.
Le caractère essentiellement unidirectionnel et ascendant de l'écoulement E peut être vérifié par la technique dite de « mesure de distribution des temps de séjour » réalisée par injection d'un traceur.The essentially unidirectional and ascending nature of the flow E can be verified by the technique known as “measurement of distribution of residence times” carried out by injection of a tracer.
Comme représenté à la figure 5, les orifices 12 peuvent être équi-répartis avec une maille sensiblement triangulaire. Ils peuvent également être équi-répartis avec une maille sensiblement carrée, comme représenté à la figure 6, ou avec une maille à base sensiblement hexagonale, comme représentée à la figure 7. D'autres répartitions géométriques des orifices 12 dans les plateaux 10 peuvent être envisagées. Les orifices 12 ne sont pas nécessairement à section circulaire, même si une telle section est privilégiée pour une raison de facilité de réalisation des plateaux 10.As shown in Figure 5, the orifices 12 can be equi-distributed with a substantially triangular mesh. They can also be equally distributed with a substantially square mesh, as shown in FIG. 6, or with a mesh with a substantially hexagonal base, as represented in FIG. 7. Other geometric distributions of the orifices 12 in the plates 10 can be considered. The orifices 12 are not necessarily of circular section, even if such a section is preferred for the reason of ease of production of the plates 10.
Les plateaux 10 peuvent être réalisés par des plaques d'épaisseur suffisante pour obtenir une résistance mécanique appropriée, les orifices 12 étant obtenus par défonçage dans le cas de plaques métalliques. Les plaques peuvent être métalliques, en céramique ou réalisées dans tout autre matériau adapté à leurs conditions d'utilisation.The plates 10 can be produced by plates of sufficient thickness to obtain resistance suitable mechanical, the orifices 12 being obtained by knocking out in the case of metal plates. The plates can be metallic, ceramic or made of any other material suited to their conditions of use.
L' invention a été décrite en référence à une réaction d'oxydation de cyclohexane. Elle n'est cependant pas limitée à cette réaction et un réacteur conforme à l'invention peut être utilisé dans toute réaction d'oxydation d'un liquide au moyen d'un gaz contenant de l'oxygène et, notamment, pour l'oxydation d'un hydrocarbure, par exemple la transformation du cumène en phénol . The invention has been described with reference to an oxidation reaction of cyclohexane. However, it is not limited to this reaction and a reactor according to the invention can be used in any reaction for the oxidation of a liquid by means of a gas containing oxygen and, in particular, for the oxidation of a hydrocarbon, for example the transformation of cumene into phenol.

Claims

REVENDICATIONS
1. Réacteur pour réaction d'oxydation d'un liquide avec un gaz contenant de l'oxygène, ledit réacteur étant alimenté uniquement en pied avec un composé à oxyder et un gaz oxydant, caractérisé en ce qu'il est divisé en étages par des plateaux séparateurs (10) pourvus d'orifices (12) de passage compatibles uniquement avec un écoulement unidirectionnel (E) du milieu réactionnel et aptes à empêcher une accumulation de gaz sous chacun desdits plateaux.1. Reactor for oxidation reaction of a liquid with an oxygen-containing gas, said reactor being supplied solely at the bottom with a compound to be oxidized and an oxidizing gas, characterized in that it is divided into stages by separator plates (10) provided with passage openings (12) compatible only with a unidirectional flow (E) of the reaction medium and capable of preventing an accumulation of gas under each of said plates.
2. Réacteur selon la revendication 1, caractérisé en ce que lesdits orifices (12) ont une section équivalente à une section circulaire de diamètre (dι2) compris entre 10 et 100 mm, de préférence entre 15 et 50 mm.2. Reactor according to claim 1, characterized in that said orifices (12) have a section equivalent to a circular section of diameter (dι 2 ) between 10 and 100 mm, preferably between 15 and 50 mm.
3. Réacteur selon l'une des revendications précédentes, caractérisé en ce que lesdits plateaux présentent un taux (ïï) d'ouverture compris entre 10 et 50%, de préférence entre 10 et 30%.3. Reactor according to one of the preceding claims, characterized in that said plates have an opening rate (ïï) of between 10 and 50%, preferably between 10 and 30%.
4. Réacteur selon l'une des revendications précédentes, caractérisé en ce que lesdits orifices (12) sont sensiblement équi-répartis sur lesdits plateaux (10) .4. Reactor according to one of the preceding claims, characterized in that said orifices (12) are substantially equi-distributed on said plates (10).
5. Réacteur selon l'une des revendications précédentes, caractérisé en ce que lesdits orifices (12) sont répartis selon une maille à base triangulaire.5. Reactor according to one of the preceding claims, characterized in that said orifices (12) are distributed in a mesh with a triangular base.
6. Réacteur selon l'une des revendications 1 à 4, caractérisé en ce que lesdits orifices (12) sont répartis selon une maille à base rectangulaire. 6. Reactor according to one of claims 1 to 4, characterized in that said orifices (12) are distributed in a mesh with a rectangular base.
7. Réacteur selon l'une des revendications 1 à 4, caractérisé en ce que lesdits orifices (12) sont répartis selon une maille à base hexagonale.7. Reactor according to one of claims 1 to 4, characterized in that said orifices (12) are distributed in a mesh with a hexagonal base.
8. Utilisation d'un réacteur (1) selon l'une des revendications précédentes pour l'oxydation d'un hydrocarbure en produit (s) tel (s) que hydroperoxyde, cétone, alcool et/ou acide.8. Use of a reactor (1) according to one of the preceding claims for the oxidation of a hydrocarbon in product (s) such as hydroperoxide, ketone, alcohol and / or acid.
9. Utilisation selon la revendication 8, pour l'oxydation de cyclohexane par de l'oxygène ou de l'air, en hydroperoxyde de cyclohexyle (HPOCH) , cyclohexanol (OL) , cyclohexanone (ONE) et/ou acide adipique.9. Use according to claim 8, for the oxidation of cyclohexane by oxygen or air, to cyclohexyl hydroperoxide (HPOCH), cyclohexanol (OL), cyclohexanone (ONE) and / or adipic acid.
10. Utilisation selon la revendication 8, pour l'oxydation de cumène en phénol. 10. Use according to claim 8, for the oxidation of cumene to phenol.
EP02795302A 2001-10-12 2002-10-11 Reactor for oxidizing reaction of a liquid with a gas Withdrawn EP1434650A1 (en)

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FR0113204A FR2830775B1 (en) 2001-10-12 2001-10-12 REACTOR FOR OXIDATION REACTION OF A LIQUID WITH A GAS
FR0113204 2001-10-12
PCT/FR2002/003466 WO2003031051A1 (en) 2001-10-12 2002-10-11 Reactor for oxidizing reaction of a liquid with a gas

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EP1434650A1 true EP1434650A1 (en) 2004-07-07

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JP2008280328A (en) * 2007-04-13 2008-11-20 Sumitomo Chemical Co Ltd Method for producing cycloalkanol and/or cycloalkanone
FR2954314B1 (en) * 2009-12-17 2012-01-27 Rhodia Operations PROCESS FOR HYDROCARBON OXIDATION BY OXYGEN
CN101972623B (en) * 2010-10-15 2012-05-23 江苏正丹化学工业股份有限公司 Continuous oxidation reaction kettle for trimethyl benzene
FR2975921A1 (en) * 2011-05-30 2012-12-07 Rhodia Poliamida E Especialidades Ltda INDUSTRIAL CHEMICAL REACTOR FOR THE CONTINUOUS PRODUCTION OF ALKYL ALKYLATE
RU2469786C1 (en) * 2011-11-03 2012-12-20 Сергей Николаевич Кузнецов Bubbling cyclohexane oxidation reactor
RU2497567C1 (en) * 2012-06-06 2013-11-10 ОТКРЫТОЕ АКЦИОНЕРНОЕ ОБЩЕСТВО "СИБУР Холдинг" Gas-fluid reactor
CN103055792B (en) * 2013-01-25 2016-04-20 浙江曙扬化工有限公司 A kind of using method of the vibration tubular reactor for cyclohexane liquid-phase oxidation
CN104028178B (en) * 2013-03-06 2016-03-02 中石化上海工程有限公司 The method of fortified water mechanics reactor mixed effect
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FR2830775A1 (en) 2003-04-18
KR20050035157A (en) 2005-04-15
CN1585672A (en) 2005-02-23
JP2006515558A (en) 2006-06-01
KR100577890B1 (en) 2006-05-10
RU2269376C2 (en) 2006-02-10
WO2003031051A1 (en) 2003-04-17
FR2830775B1 (en) 2004-08-27
UA76774C2 (en) 2006-09-15
BR0213640A (en) 2004-08-24
US20040241059A1 (en) 2004-12-02
RU2004114268A (en) 2005-05-10

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