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.

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• 2001
  • 2001-10-12 FR FR0113204A patent/FR2830775B1/fr not_active Expired - Fee Related
• 2002
  • 2002-10-11 US US10/492,287 patent/US20040241059A1/en not_active Abandoned
  • 2002-10-11 WO PCT/FR2002/003466 patent/WO2003031051A1/fr active Application Filing
  • 2002-10-11 KR KR1020047005388A patent/KR100577890B1/ko not_active IP Right Cessation
  • 2002-10-11 EP EP02795302A patent/EP1434650A1/de not_active Withdrawn
  • 2002-10-11 RU RU2004114268/15A patent/RU2269376C2/ru not_active IP Right Cessation
  • 2002-10-11 CN CNA028224329A patent/CN1585672A/zh active Pending
  • 2002-10-11 JP JP2003534075A patent/JP2006515558A/ja active Pending
  • 2002-10-11 BR BR0213640-6A patent/BR0213640A/pt not_active IP Right Cessation
  • 2002-11-10 UA UA20040402920A patent/UA76774C2/uk unknown

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