US3609176A - Process for oxidizing saturated hydrocarbons using apparatus therefor - Google Patents

Process for oxidizing saturated hydrocarbons using apparatus therefor Download PDF

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US3609176A
US3609176A US649191A US3609176DA US3609176A US 3609176 A US3609176 A US 3609176A US 649191 A US649191 A US 649191A US 3609176D A US3609176D A US 3609176DA US 3609176 A US3609176 A US 3609176A
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liquid
liquid phase
process according
phase
hydrocarbon
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Jacob Alagy
Bernard Cha
Cornelis Keon
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IFP Energies Nouvelles IFPEN
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    • 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
    • C07C29/52—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 in the presence of mineral boron compounds with, when necessary, hydrolysis of the intermediate formed
    • 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
    • B01J19/2415—Tubular reactors
    • B01J19/2425—Tubular reactors in parallel
    • 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
    • B01J19/2415—Tubular reactors
    • B01J19/2435—Loop-type reactors
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2219/00—Chemical, physical or physico-chemical processes in general; Their relevant apparatus
    • B01J2219/00049—Controlling or regulating processes
    • B01J2219/00051—Controlling the temperature
    • B01J2219/00074—Controlling the temperature by indirect heating or cooling employing heat exchange fluids
    • B01J2219/00087—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor
    • B01J2219/00103—Controlling the temperature by indirect heating or cooling employing heat exchange fluids with heat exchange elements outside the reactor in a heat exchanger separate from the reactor
    • 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
    • B01J2219/00182—Controlling or regulating processes controlling the level of reactants in the reactor vessel
    • 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
    • B01J2219/0077—Baffles attached to the reactor wall inclined
    • 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

  • FIGURE 6A 1 1111 I I, I III,
  • PRODUCT FIGURE 4 FIGURE ea IWEN'roRs M6 6 AMGY Allin/M1) (#4 (naval;
  • Oxygen is generally used at a concentration of from I to 25 percent in admixture with an inert gas such as nitrogen.
  • oxidation of cyclohexane under these conditions provides a cyclohexyl borate.
  • Other oxidizable hydrocarbons are those which contain from to 30 and preferably from five to eight carbon atoms in their molecule, for instance hexane, heptane, isooctane, decane, cyclooctane, cyclododecane, methylcyclohexane and dimethylcyclohexanes (ortho-, meta or para).
  • the oxidation temperature is usually comprised between 100 and 200 C., preferably between 140 and 190 C., the selected pressure being sufficient to maintain the hydrocarbon in the liquid phase and for example within the range of from one to 40 atmospheres.
  • the tarry products are deposited particularly at the upper part of the vessel, above the upper level of the liquid. Moreover there is observed that particles of metaboric acid are continuously drawn away by the residual gases.
  • FIG. 1 is a cross section by a vertical plane of the oxidation apparatus according to the invention.
  • FIG. 2 is an enlarged partial cross section in a horizontal plane of the same apparatus, showing in detail an injector
  • FIG. 3 is a cross section by a horizontal plane of the oxidation reaction vessel according to the invention.
  • FIG. 4 shows, in vertical cross section; the lower part of the oxidation reaction vessel according to the invention.
  • FIG. 5 sows in vertical cross section, the upper part of an oxidation reaction vessel according to the invention
  • FIG. 6A is a schematic vertical cross section of an oxidation apparatus wherein the liquid is stationary
  • FIG. 6B is a schematic vertical cross section of an oxidation apparatus, wherein the liquid is subjected to a rotational movement about a vertical axis resulting a central gas hole in the liquid;
  • FIG. 7 is a general view of 3 oxidation apparatuses, surmounted with gas washing devices.
  • a first improvement consists of carrying out the oxidation of saturated hydrocarbons having from five to eight carbon atoms per molecule, in the liqiiid phase, with the provision of a contact height Ho between said liquid phase and the oxidizing gas passing therethrough, at least equal to twice the mean diameter D of said phase, preferably at least equal to 3 times and more preferably to 5 to 15 times this mean diameter.
  • the boric reactant is a boric acid or anhydride.
  • This improving feature results in an unexpected increase in selectivity as well as in an increased conversion rate.
  • the height Ho does not seem to have any effect on the selectivity, even when said oxidation is conducted in the presence of a boron compound and by means of a molecular oxygen-containing gas, as it is the case in the present process of oxidizing saturated hydrocarbons having from five to eight carbon atoms per molecule.
  • a second improving feature which may be used in combination with the preceding one and is applicable to saturated hydrocarbons having from five to 30 carbon atoms per molecule, is characterized in that a part of the liquid phase containing the catalyst and subjected to oxidation, which is continuously withdrawn from the reaction medium, is reinjected, preferably tangentially, into said medium from a plurality of points at different levels.
  • the object of this provision is not only to provide an excellent homogenization of the reaction medium, in combination with a liquid recycling which improves the conversion rate, but also to suppress the dead zones favorable to deposit of solids as it will be clearly apparent from the description of an apparatus such as that shown in FIG. 1, which apparatus is in conformity with the principle of the invention.
  • a third improving feature in the process object of the invention consists in imparting to the liquid subjected to oxidation, a rotational movement such that the inverted cone or central airhole generated thereby has a height h comprised between 30 and percent and preferably between 40 and 70 percent of the height H of the same liquid in a stationary state.
  • An apparatus adapted for practicing the three above-mentioned improving features comprises a vertical tower or column 1 (FIG. I) having a conical bottom terminating with an outlet duct 2 for liquid products.
  • the tower bottom exhibits a strong conicity, the half-angle a at the peak of the cone being advantageously lower than 45, for example comprised between 2 and 45 and preferably of the order of 30.
  • Duct 3 conveys a gas containing molecular oxygen and more particularly air, optionally admixed with an inert gas or vapors of recycled hydrocarbon.
  • Duct 3 is placed preferably toward the basis of the cone and terminates with a conventional gas injection device into the column, for example a distributor 16 in the form of a perforated ring, the holes of which are preferably oriented toward the bottom of the column.
  • a preferred solution in view of the same purpose, consists of making use of an apparatus with a conical bottom, the walls of said bottom being perforated with holes through which the gas is injected.
  • the injection ring which terminates with the duct 3 is then no longer necessary.
  • Such a device is schematically shown: in FIG. 4.
  • the gas under pressure issuing from duct 3 fulfills the volume 17 limited by the casing l of the column and the conical walls 18 and 19 of the bottom and penetrates the liquid body as shown by the arrows 20 and 21.
  • the liquid outflow from duct 2 is aspirated by the pump P and the larger part thereof is forced through the various ducts 4, 5, 6 and 7, called stirring" ducts and is recycled into the column at different levels.
  • the stirring ducts are advantageously terminated by a narrowing, for instance injection nozzles 8 one of which is shown schematically in FIG. 2 (cross section of column 1 by a horizontal plane).
  • liquid jet is oriented tangentially to the walls of the column, so as to wash the internal surface thereof, by imparting to the liquid in the column a circular movement.
  • FIG. 1 There are shown on FIG. 1, four stirring ducts at different levels and diametrally opposite by pairs. Of course a different number of such ducts may be used according to the size of the oxidation reaction vessel. Thus there may be used for example six stirring ducts conveying the liquid at different levels and opening in the reaction vessel at angular intervals of l20 from each other.
  • FIG. 3 Such an arrangement is shown in FIG. 3 wherein duct A is placed at the level of the horizontal cross-sectional plane and ducts B and C at lower levels. The injection nozzles are not shown in this figure. The three other stirring ducts are hidden by the three former ones.
  • FIG. 1 or in FIG. 3
  • a single injection nozzle is placed at a given level
  • there may be placed two injection nozzles at the same horizontal level which corresponds to the arrangement of the simplified diagram of FIG. 3a wherein the nozzles are shown by arrows.
  • the latter duct (duct 7 in the arrangement of FIG. I) be close to the liquid-gas interface 9 and that at least the majority of the injection nozzles be so oriented as to impart to the liquid as a whole a rotational movement in one direction about a vertical axis. If this latter condition were not fulfilled, dead zones would occur within the liquid body which favor solid deposits and, as already mentioned, are detrimental to a good operation of the apparatus. Duct 7, by causing a strong stirring, prevents the formation of deposits in the vicinity of interface 9.
  • the reaction vessel shown in FIG. 1 is given by way of example; its cross section by a horizontal plane is a circle and it can be seen on FIGS. 2 and 3 that the injection nozzles are horizontal and oriented tangentially to the walls of the reaction vessel.
  • reaction vessel whose cross section in a horizontal plane is a curvilinear figure different from a circle, for instance an ellipse.
  • the liquid outflow from the reaction vessel conveyed through duct 2 is partly recycled at different levels by ducts 4 and 7 and partly supplied to a subsequent stage, for example to the hydrolysis so as to recover the oxidation products and the unconverted hydrocarbon.
  • the reaction vessel comprises at its upper part two ducts l and 11.
  • the residual gases essentially nitrogen when a mixture of nitrogen with oxygen is forced through duct 3. together with vapors of nonoxidized hydrocarbon.
  • the second duct (11) is conveyed the liquid hydrocarbon, preferably warm, used for washing the gases.
  • top of the column is provided also with a cup-shaped receiver and thereunder another on 13, funnel-shaped, in overturned position.
  • Through duct 14 is introduced the charge, optionally admixed with a part or the totality of the catalyst.
  • This charge may consist for instance of cold or heated cyclohexane which may have boric acid suspended thereinto.
  • Duct 14 opens above the interface into the gaseous phase. However it is also possible to have this duct opening within the liquid.
  • the stirring ducts 4 to 7 are provided essentially in order to maintain the solid catalyst suspended into the liquid body.
  • the flow rate through the different ducts is high, which results, at the outlet of the nozzles, in linear speeds of the liquid of, for instance, 2 to 20 meters per second, preferably 2 to 10 meters per second.
  • the stirring of the liquid is favored by gas bubbles issuing from duct 3 and distributor 16.
  • the gas escapes therefrom with a very high velocity, for instance between 10 and I00 per second, these values being however not limitative.
  • liquid hydrocarbon issuing from duct 1! through row 15, fulfills the cup 12 and runs out by overflow to the lower stage (see FIG. 5 showing only the top of the column).
  • This liquid is rejected, by the overturned funnel I3, toward the walls of the column and wash the same before reaching the interface 9 and joining the body of the reaction liquid.
  • the gases escaping from said interface follow the travel shown by the arrows in dotted line (whereas the travel of the liquid is shown by the arrows in solid line). It is seen that the gases (consisting essentially of nitrogen and hydrocarbon vapors drawing along therewith fine catalyst particles) ascend in the center of the column through the narrowing of the funnel.
  • the gases In order to escape from the reaction vessel through duct 10, the gases must pass through the substantially continuous screen formed by the washing liquid flowing down from the cup 12 and lose therein the solid particles of catalyst which they have drawn away.
  • the so-scrubbed gases escape from the column through duct 10. They may be advantageously recycled, at least partly, to the bottom of the column after their admixture with fresh air.
  • the washing liquid issuing from the duct II is preferably warm so as to avoid at this level the condensation of water which is obligatorily formed in an oxidation reaction. This water would impede, in case of oxidation of cyclohexane in the presence of boric acid, the formation of the boric ester.
  • the temperature difference between the washing liquid and the washed vapors is lower than 60 C. and preferably lower than 25 C.
  • the preferred method consists of washing the vapors with liquid hydrocarbon whose temperature is the same as that of the vapors.
  • the funnel must be placed sufficiently above the interface 9 as to avoid any projection of solid particles from the liquid body which would be otherwise deposited and form tarry products thereon. Besides, the funnel itself may be washed by a part of the liquid flowing at the center thereof.
  • More complicated embodiment of the same type may comprise a plurality of stages similar to those described above, through which a liquid phase and a gaseous phase carrying along solids, flow in countercurrent relationship so that the gases pass, at least twice, through a substantially continuous liquid stream which scrubs them, said liquid further washing the walls of the reaction vessel after leaving the lower stage.
  • the washing system shown here at the upper part of the reaction vessel 1 may be exterior thereto. Moreover, such a washing system is no more than a preferred manner of carrying out such an operation which may also be achieved with the use of other types of apparatuses such as, by way of nonlimitative examples, apparatuses of the Venturi type, or the Cyclone type as well as washing towers with filling material.
  • FIG. 1 shows a duct 22 opening downstream the pump P into the common duct through which passes the liquid which is recycled at different levels.
  • This duct may have different uses:
  • It may be used to convey to the different stirring ducts either vaporized hydrocarbon or additional liquid hydrocarbon (this later advantageously conveying acid particles) or a hydrocarbon previously used for washing the gas evolved from the body of reaction liquid.
  • FIGS. 6A and 68 respectively show a reaction vessel wherein the body of liquid of height H is stationary and another one wherein, due to the whirling movement, there is formed an inverted cone or central airhole over a height h at the center of the reaction vessel.
  • This whirling movement is of great importance since, inasmuch as it complies with the above-mentioned conditions for h/I-I, it results in the following advantages:
  • the oxidizing gas after its passage through the body of liquid where it becomes poorer in oxygen, escapes through the central cone, thereby avoiding the formation of foams which would be produced at the upper interface liquid gas 9 (FIG. 1) if the liquid was not driven in said whirling movement.
  • the ratio h/I-I of the height of the central airhole to that of the liquid body in a stationary state is comprised between 0.3 and 0.9 and preferably between 0.4 and 0.7.
  • a central airhole of the convenient size within the reaction liquid body will be easily achieved due to lateral liquid injections at different points of said body.
  • reaction vessels of the type schematically shown in FIG. 1, such reaction vessels being used either in series or in parallel with respect to the liquid outflows therefrom.
  • reaction vessels may have their own scrubbing system at the top of each one (of the type shown in FIG. 1 or of any similar type) or the gaseous outflows from the different reaction vessels may be collected in a single stream which will be washed in a single apparatus operated according to the same principle of the continuous liquid screen or to any other principle providing for the same result with regard to the removal of the solid particles.
  • a fourth improving feature in the process of oxidizing hydrocarbons having from 5 to 30 carbon atoms per molecule, and which can be advantageously combined with the three preceding ones, consists in a two-stage washing of the gaseous outflow from the oxidation zone.
  • This first stream of liquid gas at a temperature which differs by less than 60 C. and preferably by less than 25 C. from the temperature of the gases with which it is contacted.
  • the object of this first stage is not to condense the gases but to retain the solid particles and the drops of liquid phase from the reaction vessel which might have been drawn along therewith.
  • a second stage the gaseous outflow is contacted with a second steam of liquid hydrocarbon, also of the same nature as the hydrocarbon subjected to oxidation.
  • This second liquid stream is colder than the first one and may be, after contact, partially or entirely vaporized and recycled in a vaporized form to the oxidation reaction vessel.
  • the other part of the liquid may be used as washing liquid in the first stage, either as such, or after addition of fresh liquid saturated hydrocarbon of the same nature as that issuing from the first stage. It is however also possible to directly recycle this nonvaporized liquid fraction to the oxidation reaction vessel.
  • liquid hydrocarbon issued from the first washing stage it will be advantageously introduced in a liquid state in the oxidation reaction vessel.
  • FIG. 7 which shows a more complete assembly of oxidation apparatus, illustrates more particularly the fourth improving feature of the invention.
  • A, B and C are 3 oxidation reaction vessels connected in series, the liquid outflow from the first reaction vessel being conveyed to the second one through the pump P1 and the liquid outflow from the second reaction vessel being conveyed to the third one through the pump P2.
  • the oxidation product aspirated from this last reaction vessel by pump P3 is recovered from duct 109.
  • duct 99 is introduced fresh hydrocarbon to be oxidized, in the event of an insufficient flow rate through duct 98 (the object of which will be described hereinafter).
  • Through ducts 106, 107 and 108 is introduced a gas containing molecular oxygen; moreover a part of the liquid outflow from the three reaction vessels is recycled in each of them at different levels of the liquid body, through ducts such as that having the reference numeral 100.
  • the gaseous outflows from the 3 reaction vessels, conveyed through ducts 101, 102 and 103 are collected in a single gaseous stream (duct 104) which is washed in the washer D.
  • This washer is fed with the first washing liquid, i.e. with hydrocarbon of the same nature as that subjected to oxidation, which liquid is conveyed through duct 98.
  • the device which is diagrammatically illustrated by a cup and an inverted funnel and which may be replaced by any equivalent device, has for object to make easier the contact between the washing liquid and the gas to be purified.
  • liquid hydrocarbon issuing from duct 98, in first fulfills the cup placed at the upper part of the washer before overflowing on the inversed funnel which rejects it against the walls of the washer.
  • the gaseous outflow introduced into duct 104 raises in the washer D through the narrowing of the funnel and must, in order to escape from the washer through duct 105, go through the substantially continuous screen of washing liquid.
  • Through duct 110 is supplied the first washing liquid to the oxidation reaction vessel A.
  • This liquid might also be supplied to reaction vessel B or C or to a plurality of said reaction vessels.
  • Each of the three reaction vessels A, B or C may be provided with its own washing system either incorporated to the reaction vessel or not.
  • the condensation of the hydrocarbon vapors is generally low, lower than 75 percent and generally comprised between and percent due to the small temperature discrepancy between the vapors and the washing hydrocarbon supplied by duct 98.
  • This hydrocarbon is of the same nature as that subjected to the oxidation.
  • substantially all the solid impurities such as acid and boric esters particles are retained thereby. it is therefore a purified gas, issuing from line 105 which is directly contacted in an exchanger E, preferably countercurrently, with the relatively cold hydrocarbon supplied by duct 111 whose origin will be explained hereinafter and which is used as second liquid stream.
  • the gas issuing from the washer D consists essentially of nitrogen and hydrocarbon vapors.
  • a mixture of uncondensable gases with liquid is conveyed from the outlet of the condenser F through duct 113, to the decanter G wherein is effected the separation of three phases: the uncondensable gases, essentially nitrogen, which escape through duct 114 while there are obtained at the lower part of the decanter, an aqueous phase which is removed through duct 115 and an organic phase, consisting of the saturated hydrocarbon, which is recycled through duct ill to the heat exchanger E where it is contacted, as already mentioned, with still hot and washed vapors conveyed through duct 105.
  • the reheated hydrocarbon, at the outlet of the exchanger, is conveyed through duct 116 to the vaporizer H.
  • the hydrocarbon is vaporized and the so-obtained gas, evolving from the apparatus through duct 117, is injected in the 3 oxidation reaction vessels through ducts 106 107 and 108.
  • the vaporized hydrocarbon may be admixed with an oxidizing gas stream delivered by duct 8.
  • FIG. 7 The general diagram shown in FIG. 7 is no more than one example of embodiment of the invention and many modified embodiments may be considered.
  • the oxidizing gas delivered by duct 118, and which is admixed with the vaporized hydrocarbon, might issue from decanter G through duct 114.
  • still a little hot uncondensable gases essentially nitrogen
  • EXAMPLE I There is used as oxidation reaction vessel, a cylinder of stainless steel having a ratio of its height to its diameter equal to 6.
  • a reaction vessel of this type is shown in FIG. 1. it is provided with six tangential injection means for the recycling-stirring liquid, at three different levels and at its upper level with a gas scrubbing system such as shown in this figure.
  • This reaction vessel is fulfilled with cyclohexane containing suspended boric acid.
  • the liquid When stationary the liquid has a height H equal to 5 times the diameter of the reaction vessel.
  • the liquid phase is maintained at a temperature of (Y. under a pressure of 10.5 kg./cm.
  • reaction vessel In the reaction vessel are introduced continuously liquid cyclohexane at a rate of 55 liters per hour and metaboric acid (2.l kg. per hour). lnto the reaction vessel at the bottom thereof, is blowed a gaseous mixture formed of 6% (by volume) of oxygen and 94% of nitrogen.
  • the oxygen feeding rate corresponds to 960 liters per hour.
  • the liquid level is maintained constant in the reaction vessel by withdrawal of a part of the liquid outflow, at the outlet from pump P.
  • the yield is expressed in cyclohexanol cyclohexanone mixture with respect to the cyclohexane consumed in the oxidation reaction.
  • Example I is repeated in a reaction vessel of equal volume, wider but shorter. In this reaction vessel the ratio of the height of the liquid in a stationary state to the diameter is equal to 2. This new reaction vessel is also provided with six lateral liquid injections at three different levels (of course, these three levels are not so distant from each other than in the first example).
  • Example 1 is repeated but with a shorted reaction vessel wherein the ratio of the height of the liquid in a stationary state to the diameter is equal to 1.5. All other conditions being identical to those of example 1 (number of injectors, temperature, pressure, flow rates etc...), there is observed a decrease in the yield of cyclohexanol cyclohexanone and in the conversion rate respectively to 88.3% and 9.1%.
  • EXAMPLE 18 There is used a reaction vessel having the same size as that of example 1 and containing the same initial amount of cyclohexane.
  • reaction vessel is not provided with a liquidrecycling duct; the liquid phase is stirred by means of a conventional device, i.e. a rotatable blade stirrer.
  • the gaseous outflow first washed in D, is contacted, in apparatus E, with liquid cyclohexane introduced at a temperature of 40 C. (from duct 111).
  • the liquid cyclohexane issuing from contactor E is vaporized in H.
  • the so-obtained cyclohexane vapors are introduced at the base of each of the three reaction vessels, in admixture with air.
  • the liquid cyclohexane conveyed through duct 111 has been used for the scrubbing of the gases at D (i.e. duct 111 and 98 were interconnected).
  • liquid saturated hydrocarbon used for scrubbing the gaseous mixture is thereafter reinjected, at least partly, into the liquid phase subjected to oxidation, from a plurality of injection points placed at different levels of the liquid phase.
  • a process according to claim 12, wherein the height of contact between the liquid phase and the gas is comprised and comprised between about 5 and 15 times the mean diameter of the liquid phase.

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  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Physical Or Chemical Processes And Apparatus (AREA)
US649191A 1966-07-07 1967-06-27 Process for oxidizing saturated hydrocarbons using apparatus therefor Expired - Lifetime US3609176A (en)

Applications Claiming Priority (3)

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FR68651A FR1527718A (fr) 1966-07-07 1966-07-07 Procédé et appareillage d'oxydation d'hydrocarbures
FR90608A FR93064E (fr) 1966-07-07 1967-01-10 Procédé et appareillage d'oxydation d'hydrocarbures.
FR100912A FR93072E (fr) 1966-07-07 1967-03-30 Procédé et appareillage d'oxydation d'hydrocarbures.

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AT (1) AT278730B (de)
BE (1) BE700414A (de)
CH (2) CH484853A (de)
DE (1) DE1668246C3 (de)
ES (2) ES342678A1 (de)
FR (3) FR1527718A (de)
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US4550012A (en) * 1984-05-01 1985-10-29 Mobil Oil Corp. Multi-phase countercurrent reactor system
US4755281A (en) * 1984-05-01 1988-07-05 Mobil Oil Corporation Countercurrent process with froth control for treating heavy hydrocarbons
US4933508A (en) * 1987-09-24 1990-06-12 Mitsubishi Kasei Corporation Method for producing a cycloalkanol

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FR2421159A1 (fr) * 1978-03-28 1979-10-26 Inst Francais Du Petrole Procede de production d'oligomeres du propene et/ou du butene
US4413068A (en) * 1981-07-02 1983-11-01 Polysar International S.A. Hard shell soft core latex
US4450291A (en) * 1983-05-02 1984-05-22 Monsanto Company Decontamination of KA oil refinement waste stream

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US3161476A (en) * 1960-10-18 1964-12-15 Bombrini Parodi Delfino Spa Apparatus for the catalytic oxidation, in liquid phase, of organic materials
US3231413A (en) * 1960-09-28 1966-01-25 Potasse & Engrais Chimiques Method and apparatus for granulating melted solid and hardenable fluid products
US3295976A (en) * 1964-09-01 1967-01-03 Eastman Kodak Co Novel inhibitors for use in the black and white development of color reversal film
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US2938924A (en) * 1955-06-15 1960-05-31 Basf Ag Production of alcohols and ketones by the oxidation of cycloaliphatic or araliphatic hydrocarbons
US3231413A (en) * 1960-09-28 1966-01-25 Potasse & Engrais Chimiques Method and apparatus for granulating melted solid and hardenable fluid products
US3161476A (en) * 1960-10-18 1964-12-15 Bombrini Parodi Delfino Spa Apparatus for the catalytic oxidation, in liquid phase, of organic materials
US3317581A (en) * 1964-01-17 1967-05-02 Halcon International Inc Hydrocarbon oxidation process to produce borate ester
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US4755281A (en) * 1984-05-01 1988-07-05 Mobil Oil Corporation Countercurrent process with froth control for treating heavy hydrocarbons
US4933508A (en) * 1987-09-24 1990-06-12 Mitsubishi Kasei Corporation Method for producing a cycloalkanol

Also Published As

Publication number Publication date
GB1156376A (en) 1969-06-25
FR93064E (fr) 1969-02-07
FR93072E (fr) 1969-02-07
ES356682A1 (es) 1970-02-01
FR1527718A (fr) 1968-06-07
GB1157069A (en) 1969-07-02
DE1668246A1 (de) 1971-07-22
AT278730B (de) 1970-02-10
NL6709313A (de) 1968-01-08
DE1668246B2 (de) 1978-05-18
CH480280A (fr) 1969-10-31
YU34358B (en) 1979-07-10
DE1668246C3 (de) 1979-01-11
ES342678A1 (es) 1969-05-01
CH484853A (fr) 1970-01-31
BE700414A (de) 1967-12-01
YU132667A (en) 1978-12-31

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