EP0980909A1 - Hydrocarbon conversion process and its application in the hydrogenation of benzene - Google Patents

Hydrocarbon conversion process and its application in the hydrogenation of benzene Download PDF

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Publication number
EP0980909A1
EP0980909A1 EP99402025A EP99402025A EP0980909A1 EP 0980909 A1 EP0980909 A1 EP 0980909A1 EP 99402025 A EP99402025 A EP 99402025A EP 99402025 A EP99402025 A EP 99402025A EP 0980909 A1 EP0980909 A1 EP 0980909A1
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Prior art keywords
zone
distillation
level
hydrogenation
effluent
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EP99402025A
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German (de)
French (fr)
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EP0980909B1 (en
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Jean-Louis Ambrosino
Jean-Charles Viltard
Blaise Didillon
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IFP Energies Nouvelles IFPEN
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IFP Energies Nouvelles IFPEN
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/44—Hydrogenation of the aromatic hydrocarbons

Definitions

  • the invention relates to a process for converting hydrocarbons.
  • the process according to the invention combines a distillation zone with a reaction reaction zone of hydrocarbons at least partially external to the distillation zone in which one introduces an effluent comprising hydrogen. So this process allows you to convert selectively hydrocarbons separated from a hydrocarbon charge thanks to the distillation zone, in an associated reaction zone, with withdrawal from the zone distillation of the charge from the reaction zone and reintroduction of the charge converted in the distillation zone.
  • the method according to the invention applies to selective reduction the content of light unsaturated compounds (i.e. containing at most six atoms of carbon per molecule) comprising possible olefins and benzene, of a section of hydrocarbons having essentially at least 5 carbon atoms per molecule, without significant loss of the octane number.
  • light unsaturated compounds i.e. containing at most six atoms of carbon per molecule
  • benzene a section of hydrocarbons having essentially at least 5 carbon atoms per molecule
  • Benzene has carcinogenic properties and is therefore required to limit the maximum any possibility of polluting the ambient air, in particular by excluding it practically automotive fuels. In the United States reformulated fuels must not contain more than 1% by volume of benzene; in Europe it is recommended to gradually move towards this value.
  • Olefins have been recognized as among the most reactive hydrocarbons in the cycle of photochemical reactions with nitrogen oxides, which occurs in the atmosphere and which leads to the formation of ozone. An elevation of the concentration of ozone in the air can cause respiratory problems.
  • the benzene content of a gasoline is very largely dependent on that of the reformate component of this species.
  • the reformate results from a catalytic treatment naphtha for the production of aromatic hydrocarbons, comprising mainly from 6 to 9 carbon atoms in their molecule and whose index very high octane gives the essence its anti-knock properties.
  • the benzene in a reformate can be hydrogenated to cyclohexane.
  • a mixture of hydrocarbons also containing toluene and xylenes so it is necessary to fractionate beforehand this mixture so as to isolate a section containing only the benzene, which can then be hydrogenated.
  • Patent application WO 95/15 934 describes a reactive distillation which aims selectively hydrogenating diolefins and acetylenic compounds C2-C5.
  • the catalytic hydrogenation zone is completely internal to the distillation column, this which does not allow a good dissolution of the hydrogen in the charge nor of power increase the pressure.
  • the gaseous fraction containing the vaporized charge fraction and the gas stream containing hydrogen rises through said catalytic bed in gas columns.
  • the entropy of the system is strong and the loss of charge through the catalytic bed (s) is low. Therefore the way of operating according to this type of technology does not easily promote dissolution hydrogen in the liquid phase comprising the unsaturated compound (s).
  • the method according to the present invention is an improvement in the demand for Patent EP 0 781 830 A1 from the applicant, all of the characteristics of which are considered to be included in this description.
  • the invention relates to a method for converting a hydrocarbon feedstock. associating a distillation zone producing at the top a distillate and a bottom effluent, and a reaction zone at least partially external to the distillation zone. At at least one conversion reaction of at least part of at least one hydrocarbon takes place in a reaction zone comprising at least one catalytic bed, in presence of a catalyst and a gas stream comprising hydrogen.
  • Load of the reaction zone is taken at the height of at least one level of sample from the distillation zone and represents at least part of the liquid flowing into the distillation zone, and the effluent from the reaction zone is at least partly reintroduced into the distillation zone at least at a level of reintroduction, so as to ensure the continuity of the distillation.
  • the invention is characterized in that at least one from the distillation zone is withdrawn liquid effluent up to at least one racking level, at least part of said liquid effluent being at least partly treated in a separation zone lateral gas-liquid (splitter) whose gaseous effluent is at least partially reintroduced in the distillation zone and from which the liquid effluent is at least partly recovered as an intermediate cut.
  • a separation zone lateral gas-liquid (splitter) whose gaseous effluent is at least partially reintroduced in the distillation zone and from which the liquid effluent is at least partly recovered as an intermediate cut.
  • the process of the present invention makes it possible to recover at least one section of hydrocarbons at an intermediate level of the distillation zone, i.e. at a level between the bottom and the head of the distillation zone, with levels of sought-after products which can be adjusted as required, said cut being freed from most of the lighter compounds that are at least in part reintroduced into the distillation zone after separation in the lateral gas-liquid separation.
  • the method according to the invention makes it possible to separate products using the distillation area and specifically convert some compounds, under advantageous conditions of temperature and pressure, in order to recovering a distillate in which the conversion took place at the top of the distillation zone of the major part of the hydrocarbons to be converted and in order to recover at any point from the distillation zone at least one intermediate hydrocarbon fraction having the desired composition of hydrocarbons from the conversion reaction, hydrocarbons present in the charge of the distillation zone and others compounds introduced for the conversion reaction.
  • the process according to the invention applied to the hydrogenation of benzene is for example a process for treating a charge, consisting mainly of hydrocarbons containing at least 5, preferably between 5 and 9 carbon atoms per molecule, and comprising at least one unsaturated compound, comprising olefins benzene, as the said charge is treated in an area of distillation, associated with a hydrogenation reaction zone at least in part external, comprising at least one catalytic bed, in which the hydrogenation of at least part of the unsaturated compounds comprising at most six carbon atoms per molecule, i.e.
  • the method according to the invention makes it possible to withdraw an intermediate section containing for unsaturated compounds approximately the amount of benzene and light olefins desired.
  • the method according to the invention in one of its implementations, allows to directly recover a naphtha cut, i.e. a cut of light hydrocarbons, comprising mainly hydrocarbons having 5 11 carbon atoms per molecule, and reduced in benzene.
  • a naphtha cut i.e. a cut of light hydrocarbons, comprising mainly hydrocarbons having 5 11 carbon atoms per molecule, and reduced in benzene.
  • the most of the light hydrocarbons having up to 4 carbon atoms and at least part of the hydrocarbons with 5 carbon atoms per molecule.
  • the invention makes it possible to directly recover a cut usable, including approximately the amount of benzene required, and cleared of its lightest constituents, while avoiding the loss of these light constituents, by recycling of said compounds in the distillation zone.
  • the process according to the invention comprises the withdrawal of at least one liquid effluent from the distillation zone to at least one lateral gas-liquid separation zone from which comes a liquid intermediate cut and a gaseous effluent which is at least partly recycled to the distillation zone.
  • the liquid effluent to be separated can be withdrawn at at least one withdrawal level.
  • the drawdown level of the liquid effluent to be separated is generally located above the level of introduction of the charge from the distillation zone and can be any level between the level of introduction of the charge into the distillation zone and the distillation zone head level.
  • Said racking level can be located above or below the level of withdrawal of the charge from the reaction zone, above or below the level of reintroduction of effluent from the area reaction in the distillation zone.
  • the level of recycling of the gas fraction from the lateral separation zone is generally located above the level of introduction of the charge into the zone distillation.
  • Said recycling level is generally located above the level for drawing off the liquid distillate towards the lateral side separation zone.
  • Said recycling level can be located above or below the racking level of the reaction zone charge, above or below the level of reintroduction of the effluent from the reaction zone into the distillation zone.
  • the method according to the invention comprises a level of withdrawal of the liquid effluent to the lateral gas-liquid separation zone.
  • the process according to the invention comprises the recovery of a top distillate in which most of the conversion of hydrocarbons has been carried out using of the reaction zone associated with the distillation zone, said distillate therefore containing a minor part of the compounds to be converted in the reaction zone.
  • This distillate overhead can be recovered in the form of steam distillate, at least part of the steam distillate being condensed and then recycled in the distillation zone in order to ensure reflux.
  • the method comprises a stabilization zone.
  • a distillate is drawn from the distillation zone liquid stabilized at a withdrawal level located below the removal of the distillate from the head of the distillation zone. So the product you are looking for is recovered as stabilized liquid distillate, i.e. freed from most of it excess hydrogen and at least some of the light gases that are recovered in the steam distillate.
  • This recovery of the distinct liquid distillate allows eliminating by the gas distillate gases other than hydrogen present in the stream gaseous mainly comprising hydrogen introduced into the zone reaction to carry out the conversion reaction.
  • This preferred implementation makes it possible to recover several distillates: at least one stabilized distillate and at least one intermediate cut. Generally, the distillate stabilized is withdrawn at a level above the cup withdrawal level intermediate.
  • this preferred implementation in its particular application to the hydrogenation of benzene, makes it possible to recover directly by drawing off from the distillation zone a stabilized liquid distillate in which the selective hydrogenation of the benzene and any unsaturated compound comprising at most six carbon atoms per molecule and different from benzene, possibly present in the charge while limiting the hydrogenation of the C 7 + compounds (that is to say having at least seven atoms of carbon per molecule)
  • the stabilized liquid distillate contains essentially liquid compounds having at least 5 carbon atoms per molecule and usable directly as fuels.
  • the distillation zone generally comprises at least one column provided with at least minus one internal distillation chosen from the group formed by the trays, the bulk packings and structured packings, as is known to those skilled in the art profession, so that the total overall efficiency is at least equal to five floors theoretical.
  • the total overall efficiency is at least equal to five floors theoretical.
  • the charge of the distillation zone is introduced at at least one introduction level located below the level of withdrawal of the liquid towards the reaction zone, generally at a level of 2 to 40 theoretical platforms and preferably from 2 to 20 theoretical plates below the level of withdrawal of the liquid towards said zone reaction, said withdrawal level considered being the lowest.
  • the reaction zone generally comprises at least one catalytic bed, of preferably from 1 to 4 catalytic bed (s); if at least two beds are incorporated in the distillation zone, these two beds are optionally separated by at least one internal distillation.
  • the reaction zone is a zone hydrogenation.
  • the hydrogenation reaction zone performs at least partially the hydrogenation of the benzene present in the feed, generally of so that the benzene content of the stabilized liquid distillate drawn off below the level of extraction of the top distillate is at most equal to a certain content, and said reaction zone performs at least in part, preferably in major part, the hydrogenation of any unsaturated compound comprising at most six carbon atoms per molecule and different from benzene, possibly present in charge.
  • the reaction zone is at least partially external to the distillation zone.
  • the method according to the invention comprises from 1 to 6, preferably from 1 to 4 level (s) of sampling which feed (s) the external part of the zone.
  • the level of reintroduction of the converted charge at least partly in the zone external reaction is usually located substantially below, or substantially above, or substantially at the same height, at least one level of sampling, preferably of said level of sampling of the load of the zone distillation.
  • the reintroduction level is located above the levy level.
  • the reactor being at least partially external, a flow rate of liquid equal to, greater than or less than the liquid traffic of the distillation zone situated below the drawdown level of the load to be converted.
  • the flow rate of liquid withdrawn is preferably equal to or greater than the traffic liquid from the distillation zone located below the draw-off level.
  • the flow of liquid collected is preferably equal to or less than the liquid traffic in the area of distillation located below the racking level.
  • the method according to the invention makes it possible to convert a large part of (or) compound (s) to be converted outside the distillation zone possibly in pressure and / or temperature conditions different from those used in the distillation zone.
  • the process according to the invention is such that the flow of the liquid to be converted is generally co-current to the flow of the gas stream comprising hydrogen, for any catalytic bed in the external part of the reaction zone.
  • each bed catalytic is fed by a single level of sampling, preferably associated with a single level of reintroduction, said level of withdrawal being distinct from the level that feeds the other catalytic bed (s).
  • the charge at convert withdrawn from the distillation zone to the reaction zone is cooled before entering the reactor.
  • the converted charge leaving the reactor can be cooled before reintroduction into the distillation zone.
  • This cooling creates a circulating reflux.
  • one of the preferred embodiments of the invention is such that the level of reintroduction of the hydrogenated charge in the column is located above the level of withdrawal of the charge to be hydrogenated in an area where the Benzene content is the lowest. Even more preferably, the level of reintroduction is located at least 2 theoretical platforms above the level of even more preferably, the level of reintroduction of the load is located at least 4 theoretical platforms above the racking level of said charge.
  • the theoretical molar ratio of hydrogen necessary for the conversion desired benzene is 3.
  • the amount of hydrogen distributed before or in the hydrogenation zone is possibly in excess with respect to this stoichiometry, and this all the more that one must hydrogenate, in addition to the benzene present in the filler, at least partially any unsaturated compound comprising at most six atoms of carbon per molecule and present in said charge.
  • excess hydrogen if any, can be advantageously recovered for example according to one of the techniques described below.
  • the excess hydrogen which leaves the reaction zone is recovered either directly at the effluent level at the exit of the zone reaction, either in the gaseous distillate of the distillation zone, then compressed and reused in said reaction zone in order to create a reflux.
  • the excess hydrogen which leaves the reaction zone is recovered, then injected upstream of the compression stages associated with a reforming unit catalytic, mixed with hydrogen from said unit, said unit preferably operating at low pressure, i.e. generally pressure absolute less than 0.8 MPa.
  • Hydrogen included in the gas flow, used for example in the process particular of the invention for the hydrogenation of unsaturated compounds comprising at least plus six carbon atoms per molecule can come from all sources producing hydrogen at least 50% purity volume, preferably at least 80% volume of purity and even more preferably at least 90% volume of purity.
  • hydrogen from reforming processes. catalytic, methanation, P.S.A. (alternating pressure adsorption), electrochemical or steam cracking generation.
  • One of the preferred embodiments of the method according to the invention is such that the bottom effluent from the distillation is mixed at least in part with the stabilized liquid distillate recovered with a recovery level below the distillate recovery level steam.
  • the mixture thus obtained can be used as fuel either directly or by incorporation into fuel fractions.
  • the operating conditions of the part of the reaction zone internal to the zone of distillation are related to the operating conditions of the distillation.
  • Distillation is performed under absolute pressure generally between 0.1MPa and 2.5 MPa with a reflux rate of between 0.1 and 20.
  • the temperature of the distillation is between 10 and 300 ° C.
  • the liquid subjected to the conversion is mixed with a gas stream comprising hydrogen, the flow rate of which is at least equal to the stoichiometry of the conversion reactions carried out and at most equal to the flow corresponding to 10 times the stoichiometry.
  • the catalyst is placed in any catalytic bed following any technology known to those skilled in the art under operating conditions (temperature, pressure ...) independent or not, preferably independent, of operating conditions of the distillation zone.
  • operating conditions are usually the following.
  • the absolute pressure required is generally understood between 0.1 and 6 MPa.
  • the operating temperature is generally between 30 and 400 ° C.
  • the space velocity within said reaction zone, calculated with respect to with the catalyst, is generally between 0.5 and 60 h-1.
  • the flow of hydrogen corresponding to the stoichiometry of the conversion reactions carried out is understood between 1 and 10 times said stoichiometry.
  • the operating conditions are as follows.
  • the operating conditions of the part of the hydrogenation zone internal to the distillation zone are linked to the operating conditions of the distillation.
  • the distillation is carried out under an absolute pressure generally between 0.2 and 2 MPa, preferably between 0.4 and 1 MPa, with a reflux rate between 0.1 and 10, and preferably between 0.2 and 2.
  • the zone head temperature is generally between 30 and 180 ° C and the zone bottom temperature is generally between 120 and 280 ° C.
  • the hydrogenation reaction is carried out under conditions which are most generally intermediate between those established at the head and at the bottom of the distillation zone, at a temperature between 100 and 200 ° C., and preferably between 120 and 180 ° C. , and at an absolute pressure of between 0.2 and 3 MPa, preferably between 0.4 and 2 MPa.
  • the liquid subjected to hydrogenation is mixed with a gas stream comprising hydrogen, the flow rate of which depends on the concentration of benzene in said liquid and, more generally, unsaturated compounds containing at most six carbon atoms per molecule of the charge. from the distillation zone.
  • the hydrogen flow rate is generally at least equal to the flow rate corresponding to the stoichiometry of the hydrogenation reactions carried out (hydrogenation of benzene and of the other unsaturated compounds containing at most six carbon atoms per molecule, included in the hydrogenation charge) and at most equal to the flow rate corresponding to 10 times the stoichiometry, preferably between 1 and 6 times the stoichiometry, even more preferably between 1 and 3 times the stoichiometry.
  • the absolute pressure required for this hydrogenation step is generally between 0.1 and 6 MPa absolute, preferably between 0.2 and 5 MPa and even more preferably between 0.5 and 3.5 MPa.
  • the temperature of the hydrogenation zone is generally between 100 and 400 ° C, preferably between 120 and 350 ° C and preferably between 140 and 320 ° C.
  • the space velocity within said hydrogenation zone, calculated with respect to the catalyst, is generally between 1 and 60 and more particularly between 1 and 40 h -1 (volume flow rate of charge per volume of catalyst).
  • the hydrogen flow rate corresponding to the stoichiometry of the hydrogenation reactions carried out is between 1 and 10 times said stoichiometry, preferably between 1 and 6 times said stoichiometry and even more preferably between 1 and 3 times said stoichiometry.
  • the temperature and pressure conditions can also, within the scope of the process of the present invention, be between those which are established at the top and at the bottom of the distillation zone.
  • the rate of reflux means the ratio of the flow mass of the reflux on the mass flow rate of the column.
  • the catalyst used in the area hydrogenation generally comprises at least one metal chosen from the group VIII, preferably chosen from the group formed by nickel and platinum, used as such which or preferably deposited on a support.
  • the metal should generally be found in reduced form at least for 50% by weight of its totality. But any other hydrogenation catalyst known to those skilled in the art can also be chosen.
  • the proportion of nickel relative to the total weight of catalyst is between 5 and 70%, more particularly between 10 and 70% and preferably between 15 and 65%.
  • a catalyst is generally used such that the average size of the nickel crystallites is less than 100.10 -10 m, preferably less than 80.10 -10 m, even more preferably less than 60.10 -10 m.
  • the support is generally chosen from the group formed by alumina, silica-aluminas, silica, zeolites, activated carbon, clays, aluminous cements, rare earth oxides and alkaline earth oxides, alone or in mixture.
  • a support based on alumina or silica is preferably used, with a specific surface area of between 30 and 300 m 2 / g, preferably between 90 and 260 m 2 / g.
  • Figure 1 is an illustration of a possibility of carrying out the method according to the invention.
  • the hydrocarbon charge is sent to column 2 by line 1.
  • Said column contains internal distillation, which is for example in the case represented in FIG. 1 of the plates or of the lining, represented in part by dotted lines in said figure.
  • the least volatile fraction of the reformate is recovered by the line 5, a part is reboiled in the exchanger 6 and a part is evacuated via line 7.
  • Reboiling steam is reintroduced into the column by line 8.
  • the distillate stabilized liquid is extracted by line 18, the steam distillate is sent by line 9 in a condenser 10 then in a flask 11 from which the steam distillate is extracted by the line 14.
  • the liquid phase of the balloon 11 is partially returned via line 12, in column head to reflux, and another part of the liquid phase can be picked up by line 13.
  • the liquid effluent to be separated is withdrawn from the distillation zone by line 19, then sent to a gas-liquid side separation zone (20), from which it is recycled the gaseous effluent in the distillation zone via line 21 and a section is recovered intermediate through line 23, part of the section is rewashed in the exchanger 22.
  • the process has a configuration with withdrawal of a liquid effluent to a lateral gas-liquid separation zone, with reintroduction of the gaseous effluent into the distillation and recovery zone of the liquid effluent as an intermediate cut.
  • the unit is shown in Figure 1.
  • the process has a configuration with withdrawal of a liquid effluent stabilized in below the racking of a steam distillate and with a level of reintroduction of the hydrogenated charge 9 trays above the racking tray.
  • the column includes 57 theoretical plates (including condenser and reboiler) and has a diameter of 3.35 m.
  • the associated side column has 7 theoretical plates (including the reboiler).
  • the reflux rate relative to food is 1.02.
  • the reboiling power is 12800 kW.
  • the power of the side column reboiler is 271 kW.
  • the process is carried out with an external hydrogenation reactor containing 7 m 3 of catalyst and operating at an absolute pressure of 1.5 MPa.
  • the nickel catalyst is sold by the company PROCATALYSE under the reference LD746.
  • the stabilized liquid effluent is recovered (light reformate) at plate 3 via line 18 and the steam distillate at the top of the column via line 14.
  • the charge for the column is injected by line 1 into plate 37.
  • the charge for reactor 3 is withdrawn from tray 30 via line 15.
  • Hydrogen is introduced via line 4 before entering the reactor operating in downflow and at 1.5 MPa pressure absolute.
  • the hydrogen / benzene molar ratio is 2.63.
  • the effluent from reactor 3 is cooled and then re-injected into the column via line 17 on plate 21.
  • the pressure absolute at the reflux flask is 0.75 MPa.
  • the method according to the present invention where there is withdrawal of a liquid distillate treated in a lateral separation zone makes it possible to recover a directly usable intermediate cut.
  • the cut intermediate is a naphtha cut comprising approximately 3.8% by volume of benzene.
  • the light reformate (18) contains 0.35% by volume of benzene
  • the heavy reformate (7) contains 0.6% volume of benzene.
  • the REID vapor pressure of naphtha is 0.086 MPa
  • that of the mixture constituted by the light reformate and the heavy reformate is 0.022 MPa.

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  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Vaporization, Distillation, Condensation, Sublimation, And Cold Traps (AREA)

Abstract

Hydrocarbon charge is treated in a distillation zone associated with a reaction zone that is partially or totally external and comprises at least one catalytic bed for catalytic conversion of at least a part of at least one hydrocarbon in the presence of a catalyst and a flow of gaseous hydrogen. Potentially harmful levels of benzene and lower olefin contents can be removed. The reaction zone charge is withdrawn at a height of at least one discharge level and represents at least part of the liquid passing through the distillation zone. At least part of the effluent of the reaction zone is reintroduced into the distillation zone at a height of at least one reintroduction level so as to ensure continuous distillation. Effluent fluid is extracted from the distillation zone at a height of at least one level of extraction. At least part of the effluent is at least partially treated in a gas-liquid lateral separation zone. The separated gaseous effluent is at least partially reintroduced into the distillation zone, and the liquid effluent is at least partially recovered as an intermediate cut.

Description

L'invention concerne un procédé de conversion d'hydrocarbures. Le procédé selon l'invention associe une zone de distillation à une zone réactionnelle de conversion d'hydrocarbures au moins en partie externe à la zone de distillation dans laquelle on introduit un effluent comprenant de l'hydrogène. Ainsi ce procédé permet de convertir sélectivement des hydrocarbures séparés d'une charge d'hydrocarbures grâce à la zone de distillation, dans une zone réactionnelle associée, avec soutirage de la zone de distillation de la charge de la zone réactionnelle et réintroduction de la charge convertie dans la zone de distillation.The invention relates to a process for converting hydrocarbons. The process according to the invention combines a distillation zone with a reaction reaction zone of hydrocarbons at least partially external to the distillation zone in which one introduces an effluent comprising hydrogen. So this process allows you to convert selectively hydrocarbons separated from a hydrocarbon charge thanks to the distillation zone, in an associated reaction zone, with withdrawal from the zone distillation of the charge from the reaction zone and reintroduction of the charge converted in the distillation zone.

Plus particulièrement, le procédé selon l'invention s'applique à la réduction sélective de la teneur en composés insaturés légers (c'est-à-dire contenant au plus six atomes de carbone par molécule) comportant des oléfines éventuelles et du benzène, d'une coupe d'hydrocarbures comportant essentiellement au moins 5 atomes de carbone par molécule, sans perte sensible de l'indice d'octane.More particularly, the method according to the invention applies to selective reduction the content of light unsaturated compounds (i.e. containing at most six atoms of carbon per molecule) comprising possible olefins and benzene, of a section of hydrocarbons having essentially at least 5 carbon atoms per molecule, without significant loss of the octane number.

En effet, compte tenu de la nocivité reconnue du benzène et des oléfines, composés insaturés, la tendance générale est de réduire la teneur de ces constituants dans les essences.Indeed, given the recognized harmfulness of benzene and olefins, compounds the general tendency is to reduce the content of these constituents in the essences.

Le benzène a des propriétés cancérigènes et il est par conséquent exigé de limiter au maximum toute possibilité de polluer l'air ambiant, notamment en l'excluant pratiquement des carburants automobiles. Aux Etats-Unis les carburants reformulés ne doivent pas contenir plus de 1% en volume de benzène; en Europe, il est préconisé de tendre progressivement vers cette valeur.Benzene has carcinogenic properties and is therefore required to limit the maximum any possibility of polluting the ambient air, in particular by excluding it practically automotive fuels. In the United States reformulated fuels must not contain more than 1% by volume of benzene; in Europe it is recommended to gradually move towards this value.

Les oléfines ont été reconnues comme étant parmi les hydrocarbures les plus réactifs dans le cycle de réactions photochimiques avec les oxydes d'azote, qui se produit dans l'atmosphère et qui conduit à la formation d'ozone. Une élévation de la concentration d'ozone dans l'air peut être source de troubles respiratoires. La diminution de la teneur en oléfines des essences, et plus particulièrement des oléfines les plus légères qui ont le plus tendance à se volatiliser lors des manipulations du carburant, est par conséquent souhaitable.Olefins have been recognized as among the most reactive hydrocarbons in the cycle of photochemical reactions with nitrogen oxides, which occurs in the atmosphere and which leads to the formation of ozone. An elevation of the concentration of ozone in the air can cause respiratory problems. The reduction in the olefin content of gasolines, and more particularly of olefins the lightest which have the most tendency to volatilize when handling the fuel, is therefore desirable.

La teneur en benzène d'une essence est très largement dépendante de celle de la composante réformat de cette essence. Le réformat résulte d'un traitement catalytique de naphta destiné à produire des hydrocarbures aromatiques, comprenant principalement de 6 à 9 atomes de carbone dans leur molécule et dont l'indice d'octane très élevé confère à l'essence ses propriétés antidétonantes.The benzene content of a gasoline is very largely dependent on that of the reformate component of this species. The reformate results from a catalytic treatment naphtha for the production of aromatic hydrocarbons, comprising mainly from 6 to 9 carbon atoms in their molecule and whose index very high octane gives the essence its anti-knock properties.

Pour les raisons de nocivité décrites ci-dessus, il est donc nécessaire de réduire au maximum la teneur en benzène du réformat.For the reasons of harmfulness described above, it is therefore necessary to reduce to maximum the benzene content of the reformate.

Le benzène d'un réformat peut être hydrogéné en cyclohexane. Comme il est impossible d'hydrogéner sélectivement le benzène d'un mélange d'hydrocarbures contenant également du toluène et des xylènes, il est donc nécessaire de fractionner préalablement ce mélange de manière à isoler une coupe ne contenant que le benzène, qui peut alors être hydrogéné.The benzene in a reformate can be hydrogenated to cyclohexane. As he is impossible to selectively hydrogenate benzene from a mixture of hydrocarbons also containing toluene and xylenes, so it is necessary to fractionate beforehand this mixture so as to isolate a section containing only the benzene, which can then be hydrogenated.

La demande de brevet WO 95/15 934 décrit une distillation réactive qui a pour but d'hydrogéner sélectivement les dioléfines et les composés acétyléniques C2-C5. La zone catalytique d'hydrogénation est totalement interne à la colonne de distillation, ce qui ne permet pas une bonne dissolution de l'hydrogène dans la charge ni de pouvoir augmenter la pression.Patent application WO 95/15 934 describes a reactive distillation which aims selectively hydrogenating diolefins and acetylenic compounds C2-C5. The catalytic hydrogenation zone is completely internal to the distillation column, this which does not allow a good dissolution of the hydrogen in the charge nor of power increase the pressure.

Il a été décrit plusieurs procédés dans lesquels la zone catalytique d'hydrogénation du benzène est interne à la colonne de distillation qui sépare le benzène des autres composés aromatiques, ce qui permet de réaliser une économie d'appareillage. De tels procédés sont décrits dans les brevets US 4.232.177, US 4.307.254 et US 4.336.407, US 3.629.478, US 4.471.154, et US 3.629.478. Il est apparu que la perte de charge au travers du ou des lit(s) catalytique(s) selon ces procédés ne permet pas l'obtention d'un mélange intime entre la phase liquide et le flux gazeux contenant de l'hydrogène. En effet, selon ce type de technologie où la réaction et la distillation procèdent simultanément dans le même espace physique, la phase liquide descend à travers tout lit catalytique de la zone réactionnelle en écoulement ruisselant, donc en filets de liquide. La fraction gazeuse contenant la fraction de charge vaporisée et le flux gazeux contenant de l'hydrogène monte au travers dudit lit catalytique dans des colonnes de gaz. Par cette disposition, l'entropie du système est forte et la perte de charge à travers le (ou les) lit(s) catalytique(s) est faible. Par suite la façon d'opérer selon ce type de technologie ne permet pas facilement de promouvoir la dissolution de l'hydrogène dans la phase liquide comprenant le ou les composé(s) insaturé(s).Several processes have been described in which the catalytic hydrogenation zone of benzene is internal to the distillation column which separates benzene from the others aromatic compounds, which saves equipment. Of such processes are described in patents US 4,232,177, US 4,307,254 and US 4,336,407, US 3,629,478, US 4,471,154, and US 3,629,478. It appeared that the loss charge through the catalytic bed (s) according to these methods does not allow obtaining an intimate mixture between the liquid phase and the gas flow containing hydrogen. Indeed, according to this type of technology where the reaction and the distillation proceed simultaneously in the same physical space, the liquid phase descends to through any catalytic bed of the reaction zone in flowing flow, therefore in liquid fillets. The gaseous fraction containing the vaporized charge fraction and the gas stream containing hydrogen rises through said catalytic bed in gas columns. By this arrangement, the entropy of the system is strong and the loss of charge through the catalytic bed (s) is low. Therefore the way of operating according to this type of technology does not easily promote dissolution hydrogen in the liquid phase comprising the unsaturated compound (s).

Il a été décrit plusieurs procédés dans lesquels la zone de réaction est extérieure à la colonne de distillation avec soutirage de la charge à convertir à un niveau de la colonne et réintroduction de l'effluent converti dans la colonne. De tels procédés sont décrits dans le brevet US 4.503.265 et dans les demandes WO 93/19 031, WO 93/19 032, WO 94/13 599 pour une application en synthèse d'alkyléthers. De même, le brevet US 5.177.283 décrit cette technique pour l'akylation d'hydrocarbures aromatiques.Several processes have been described in which the reaction zone is outside the distillation column with withdrawal of the charge to be converted at a level of the column and reintroduction of the converted effluent into the column. Such methods are described in US patent 4,503,265 and in applications WO 93/19 031, WO 93/19 032, WO 94/13 599 for an application in the synthesis of alkyl ethers. Likewise, the US Patent 5,177,283 describes this technique for the akylation of hydrocarbons aromatic.

La demande de brevet de la demanderesse EP 0 781 830 A1 décrit un procédé d'hydrogénation du benzène dans lequel on utilise un colonne de distillation associée à une zone réactionnelle au moins en partie externe. La charge de la zone réactionnelle est soutirée de la zone de distillation vers la zone réactionnelle, l'effluent de la zone réactionnelle étant réintroduit dans la zone de distillation. On récupère un distillat de tête de zone de distillation et un réformat de fond de zone de distillation.The patent application of the applicant EP 0 781 830 A1 describes a process of hydrogenation of benzene in which an associated distillation column is used to a reaction zone at least partly external. The charge of the area is withdrawn from the distillation zone towards the reaction zone, the effluent of the reaction zone being reintroduced into the distillation zone. We recover a distillation head of distillation and a bottom reform of distillation zone.

Le procédé selon la présente invention est un perfectionnement de la demande de brevet EP 0 781 830 A1 de la demanderesse dont toutes les caractéristiques sont considérées comme incluses dans la présente description.The method according to the present invention is an improvement in the demand for Patent EP 0 781 830 A1 from the applicant, all of the characteristics of which are considered to be included in this description.

L'invention concerne un procédé de conversion d'une charge d'hydrocarbures associant une zone de distillation produisant en tête un distillat et un effluent de fond, et une zone réactionnelle au moins en partie externe à la zone de distillation. Au moins une réaction de conversion d'au moins une partie d'au moins un hydrocarbure a lieu dans une zone réactionnelle comprenant au moins un lit catalytique, en présence d'un catalyseur et d'un flux gazeux comprenant de l'hydrogène. La charge de la zone réactionnelle est prélevée à la hauteur d'au moins un niveau de prélèvement de la zone de distillation et représente au moins une partie du liquide coulant dans la zone de distillation, et l'effluent de la zone réactionnelle est au moins en partie réintroduit dans la zone de distillation à la hauteur d'au moins un niveau de réintroduction, de manière à assurer la continuité de la distillation. L'invention est caractérisée en ce qu'on soutire en outre de la zone de distillation au moins un effluent liquide à la hauteur d'au moins un niveau de soutirage, au moins une partie dudit effluent liquide étant au moins en partie traitée dans une zone de séparation latérale gaz-liquide (splitter) dont l'effluent gazeux est au moins en partie réintroduit dans la zone de distillation et dont l'effluent liquide est au moins en partie récupéré comme coupe intermédiaire.The invention relates to a method for converting a hydrocarbon feedstock. associating a distillation zone producing at the top a distillate and a bottom effluent, and a reaction zone at least partially external to the distillation zone. At at least one conversion reaction of at least part of at least one hydrocarbon takes place in a reaction zone comprising at least one catalytic bed, in presence of a catalyst and a gas stream comprising hydrogen. Load of the reaction zone is taken at the height of at least one level of sample from the distillation zone and represents at least part of the liquid flowing into the distillation zone, and the effluent from the reaction zone is at least partly reintroduced into the distillation zone at least at a level of reintroduction, so as to ensure the continuity of the distillation. The invention is characterized in that at least one from the distillation zone is withdrawn liquid effluent up to at least one racking level, at least part of said liquid effluent being at least partly treated in a separation zone lateral gas-liquid (splitter) whose gaseous effluent is at least partially reintroduced in the distillation zone and from which the liquid effluent is at least partly recovered as an intermediate cut.

Ainsi le procédé de la présente invention permet de récupérer au moins une coupe d'hydrocarbures à un niveau intermédiaire de la zone de distillation, c'est à dire à un niveau compris entre le fond et la tête de la zone de distillation, avec des teneurs en produits recherchés qui peuvent être ajustées selon les besoins, ladite coupe étant débarrassée de la majeure partie des composés les plus légers qui sont au moins en partie réintroduits dans la zone de distillation après séparation dans la zone de séparation latérale gaz-liquide. En effet, par l'association d'une zone de distillation et d'une une zone réactionnelle, le procédé selon l'invention permet de séparer des produits à l'aide de la zone de distillation et de convertir spécifiquement certains composés, dans des conditions avantageuses de température et de pression, afin de récupérer en tête de zone de distillation un distillat dans lequel a eu lieu la conversion de la majeure partie des hydrocarbures à convertir et afin de récupérer en tout point de la zone de distillation au moins une fraction d'hydrocarbures intermédiaire ayant la composition voulue en hydrocarbures issus de la réaction de conversion, en hydrocarbures présents dans la charge de la zone de distillation et en autres composés introduits pour la réaction de conversion.Thus the process of the present invention makes it possible to recover at least one section of hydrocarbons at an intermediate level of the distillation zone, i.e. at a level between the bottom and the head of the distillation zone, with levels of sought-after products which can be adjusted as required, said cut being freed from most of the lighter compounds that are at least in part reintroduced into the distillation zone after separation in the lateral gas-liquid separation. Indeed, by the association of a distillation zone and of a reaction zone, the method according to the invention makes it possible to separate products using the distillation area and specifically convert some compounds, under advantageous conditions of temperature and pressure, in order to recovering a distillate in which the conversion took place at the top of the distillation zone of the major part of the hydrocarbons to be converted and in order to recover at any point from the distillation zone at least one intermediate hydrocarbon fraction having the desired composition of hydrocarbons from the conversion reaction, hydrocarbons present in the charge of the distillation zone and others compounds introduced for the conversion reaction.

L'application particulière du procédé selon l'invention à un procédé de réduction de la teneur en benzène d'une charge d'hydrocarbures permet de produire à partir d'un réformat brut, un réformat appauvri en benzène ou, si nécessaire, quasi totalement épuré de benzène, ainsi que d'autres hydrocarbures insaturés contenant au plus six atomes de carbone par molécule tels que les oléfines légères, et au moins un réformat comprenant la quantité souhaitée de benzène et autres hydrocarbures insaturés, sans perte significative de rendement, tout en limitant l'hydrogenation des composés C7 + (c'est-à-dire ayant au moins sept atomes de carbone par molécule).The particular application of the process according to the invention to a process for reducing the benzene content of a hydrocarbon charge makes it possible to produce, from a crude reformate, a reformate depleted in benzene or, if necessary, almost completely stripped of benzene, as well as other unsaturated hydrocarbons containing at most six carbon atoms per molecule such as light olefins, and at least one reformate comprising the desired amount of benzene and other unsaturated hydrocarbons, without significant loss of yield, while limiting the hydrogenation of C 7 + compounds (that is to say having at least seven carbon atoms per molecule).

Le procédé selon l'invention appliqué à l'hydrogénation du benzène est par exemple un procédé de traitement d'une charge, constituée en majeure partie par des hydrocarbures comportant au moins 5, de préférence entre 5 et 9 atomes de carbone par molécule, et comprenant au moins un composé insaturé, comportant des oléfines éventuelles et du benzène, tel que l'on traite ladite charge dans une zone de distillation, associée à une zone réactionnelle d'hydrogénation au moins en partie externe, comprenant au moins un lit catalytique, dans laquelle on réalise l'hydrogénation d'au moins une partie des composés insaturés comprenant au plus six atomes de carbone par molécule, c'est-à-dire comprenant jusqu'à six (inclus) atomes de carbone par molécule, et contenus dans la charge, en présence d'un catalyseur d'hydrogénation et d'un flux gazeux comprenant, de préférence en majeure partie, de l'hydrogène, la charge de la zone réactionnelle étant prélevée à la hauteur d'un niveau de prélèvement et représentant au moins une partie, de préférence la majeure partie, du liquide coulant dans la zone de distillation, l'effluent de la zone réactionnelle étant au moins en partie, de préférence en majeure partie, réintroduit dans la zone de distillation à la hauteur d'au moins un niveau de réintroduction, de manière à assurer la continuité de la distillation, ledit procédé étant caractérisé en ce qu'on soutire en outre de la zone de distillation au moins un effluent liquide à la hauteur d'au moins un niveau de soutirage, au moins une partie dudit effluent liquide étant au moins en partie traitée dans une zone de séparation latérale gaz-liquide (splitter), dont l'effluent gazeux est au moins en partie réintroduit dans la zone de distillation et dont l'effluent liquide est au moins en partie récupéré comme coupe intermédiaire.The process according to the invention applied to the hydrogenation of benzene is for example a process for treating a charge, consisting mainly of hydrocarbons containing at least 5, preferably between 5 and 9 carbon atoms per molecule, and comprising at least one unsaturated compound, comprising olefins benzene, as the said charge is treated in an area of distillation, associated with a hydrogenation reaction zone at least in part external, comprising at least one catalytic bed, in which the hydrogenation of at least part of the unsaturated compounds comprising at most six carbon atoms per molecule, i.e. including up to six (inclusive) carbon atoms per molecule, and contained in the charge, in the presence of a hydrogenation catalyst and a gas stream comprising, preferably in major part, of hydrogen, the charge of the reaction zone being taken at the height a level of levy and representing at least a part, preferably the most of the liquid flowing in the distillation zone, the effluent from the zone being at least partly, preferably mainly, reintroduced in the distillation zone at the level of at least one reintroduction level, so as to ensure the continuity of the distillation, said process being characterized in that at least one liquid effluent is withdrawn from the distillation zone at the height of at least one withdrawal level, at least part of said liquid effluent being at least partly treated in a gas-liquid lateral separation zone (splitter), the gaseous effluent of which is at least partially reintroduced into the distillation and whose liquid effluent is at least partly recovered as a cut intermediate.

Le procédé selon l'invention permet de soutirer une coupe intermédiaire contenant pour les composés insaturés environ la quantité de benzène et d'oléfines légères désirée. Par exemple le procédé selon l'invention, dans l'une de ses mises en oeuvre, permet de récupérer directement une coupe naphta, c'est à dire une coupe d'hydrocarbures légère, comportant en majeure partie des hydrocarbures ayant de 5 à 11 atomes de carbone par molécule, et allégée en benzène. Dans cet exemple, la coupe intermédiaire récupérée est débarrassée de la majeure partie des hydrocarbures légers ayant jusqu'à 4 atomes de carbone et d'au moins une partie des hydrocarbures ayant 5 atomes de carbone par molécule.The method according to the invention makes it possible to withdraw an intermediate section containing for unsaturated compounds approximately the amount of benzene and light olefins desired. For example, the method according to the invention, in one of its implementations, allows to directly recover a naphtha cut, i.e. a cut of light hydrocarbons, comprising mainly hydrocarbons having 5 11 carbon atoms per molecule, and reduced in benzene. In this example, the most of the light hydrocarbons having up to 4 carbon atoms and at least part of the hydrocarbons with 5 carbon atoms per molecule.

Ainsi, dans le cas de l'application du procédé de l'invention à la réduction de la teneur en benzène d'un réformat, l'invention permet de récupérer directement une coupe utilisable, comprenant environ la quantité de benzène nécessaire, et débarrassée de ses constituants les plus légers, tout en évitant la perte de ces constituants légers, par recyclage desdits composés dans la zone de distillation.Thus, in the case of the application of the process of the invention to the reduction of the content in reformed benzene, the invention makes it possible to directly recover a cut usable, including approximately the amount of benzene required, and cleared of its lightest constituents, while avoiding the loss of these light constituents, by recycling of said compounds in the distillation zone.

Ainsi le procédé selon l'invention comprend le soutirage d'au moins un effluent liquide de la zone de distillation vers au moins une zone de séparation latérale gaz-liquide d'où est issue une coupe intermédiaire liquide et un effluent gazeux qui est au moins en partie recyclé vers la zone de distillation.Thus the process according to the invention comprises the withdrawal of at least one liquid effluent from the distillation zone to at least one lateral gas-liquid separation zone from which comes a liquid intermediate cut and a gaseous effluent which is at least partly recycled to the distillation zone.

L'effluent liquide à séparer peut être soutiré à au moins un niveau de soutirage. Le niveau de soutirage de l'effluent liquide à séparer est généralement situé au-dessus du niveau d'introduction de la charge de la zone de distillation et peut être tout niveau compris entre le niveau d'introduction de la charge dans la zone de distillation et le niveau tête de zone de distillation. Ledit niveau de soutirage peut être situé au-dessus ou en dessous du niveau de soutirage de la charge de la zone réactionnelle, au-dessus ou au-dessous du niveau de réintroduction de l'effluent de la zone réactionnelle dans la zone de distillation.The liquid effluent to be separated can be withdrawn at at least one withdrawal level. The drawdown level of the liquid effluent to be separated is generally located above the level of introduction of the charge from the distillation zone and can be any level between the level of introduction of the charge into the distillation zone and the distillation zone head level. Said racking level can be located above or below the level of withdrawal of the charge from the reaction zone, above or below the level of reintroduction of effluent from the area reaction in the distillation zone.

Le niveau de recyclage de la fraction gazeuse issue de la zone de séparation latérale est généralement situé au-dessus du niveau d'introduction de la charge dans la zone de distillation. Ledit niveau de recyclage est généralement situé au-dessus du niveau de soutirage du distillat liquide vers la zone latérale de séparation latérale. Ledit niveau de recyclage peut être situé au-dessus ou au-dessous du niveau de soutirage de la charge de la zone réactionnelle, au-dessus ou au-dessous du niveau de réintroduction de l'effluent de la zone réactionnelle dans la zone de distillation.The level of recycling of the gas fraction from the lateral separation zone is generally located above the level of introduction of the charge into the zone distillation. Said recycling level is generally located above the level for drawing off the liquid distillate towards the lateral side separation zone. Said recycling level can be located above or below the racking level of the reaction zone charge, above or below the level of reintroduction of the effluent from the reaction zone into the distillation zone.

De manière préférée, le procédé selon l'invention comporte un niveau de soutirage de l'effluent liquide vers la zone de séparation latérale gaz-liquide.Preferably, the method according to the invention comprises a level of withdrawal of the liquid effluent to the lateral gas-liquid separation zone.

Outre la récupération d'une coupe intermédiaire soutirée à tout niveau de la zone de distillation, le procédé selon l'invention comprend la récupération d'un distillat de tête dans lequel on a réalisé en majeure partie la conversion d'hydrocarbures au moyen de la zone réactionnelle associée à la zone de distillation, ledit distillat contenant donc une mineure partie des composés à convertir dans la zone réactionnelle. Ce distillat de tête peut être récupéré sous forme de distillat vapeur, au moins une partie du distillat vapeur étant condensée puis recyclée dans la zone de distillation afin d'en assurer le reflux.In addition to the recovery of an intermediate cut drawn at any level of the distillation, the process according to the invention comprises the recovery of a top distillate in which most of the conversion of hydrocarbons has been carried out using of the reaction zone associated with the distillation zone, said distillate therefore containing a minor part of the compounds to be converted in the reaction zone. This distillate overhead can be recovered in the form of steam distillate, at least part of the steam distillate being condensed and then recycled in the distillation zone in order to ensure reflux.

Dans une mise en oeuvre préférée du procédé selon l'invention, le procédé comprend une zone de stabilisation. Dans ce cas, on soutire de la zone de distillation un distillat liquide stabilisé à un niveau de prélèvement situé en-dessous du niveau de prélèvement du distillat de tête de zone de distillation. Ainsi le produit recherché est récupéré comme distillat liquide stabilisé, c'est-à-dire débarrassé de la majeure partie de l'hydrogène en excès et au moins en partie des gaz légers qui sont récupérés dans le distillat vapeur. Cette récupération du distillat liquide disctincte permet d'éliminer par le distillat gazeux les gaz autres que l'hydrogène présents dans le flux gazeux comprenant en majeure partie de l'hydrogène introduit dans la zone réactionnelle pour effectuer la réaction de conversion. In a preferred implementation of the method according to the invention, the method comprises a stabilization zone. In this case, a distillate is drawn from the distillation zone liquid stabilized at a withdrawal level located below the removal of the distillate from the head of the distillation zone. So the product you are looking for is recovered as stabilized liquid distillate, i.e. freed from most of it excess hydrogen and at least some of the light gases that are recovered in the steam distillate. This recovery of the distinct liquid distillate allows eliminating by the gas distillate gases other than hydrogen present in the stream gaseous mainly comprising hydrogen introduced into the zone reaction to carry out the conversion reaction.

Cette mise en oeuvre préférée permet de récupérer plusieurs distillats : au moins un distillat stabilisé et au moins une coupe intermédiaire. Généralement, le distillat stabilisé est soutiré à un niveau situé au-dessus du niveau de soutirage de la coupe intermédiaire.This preferred implementation makes it possible to recover several distillates: at least one stabilized distillate and at least one intermediate cut. Generally, the distillate stabilized is withdrawn at a level above the cup withdrawal level intermediate.

Ainsi, par exemple, cette mise en oeuvre préférée, dans son application particulière à l'hydrogénation du benzène, permet de récupérer directement par soutirage de la zone de distillation un distillat liquide stabilisé dans lequel on a réalisé au moins partiellement l'hydrogénation sélective du benzène et de tout composé insaturé comprenant au plus six atomes de carbone par molécule et différent du benzène, éventuellement présent dans la charge tout en limitant l'hydrogenation des composés C7 + (c'est-à-dire ayant au moins sept atomes de carbone par molécule)Thus, for example, this preferred implementation, in its particular application to the hydrogenation of benzene, makes it possible to recover directly by drawing off from the distillation zone a stabilized liquid distillate in which the selective hydrogenation of the benzene and any unsaturated compound comprising at most six carbon atoms per molecule and different from benzene, possibly present in the charge while limiting the hydrogenation of the C 7 + compounds (that is to say having at least seven atoms of carbon per molecule)

Dans le cas de l'hydrogénation du benzène, le distillat liquide stabilisé contient essentiellement des composés liquides ayant au moins 5 atomes de carbones par molécule et utilisables directement comme carburants.In the case of hydrogenation of benzene, the stabilized liquid distillate contains essentially liquid compounds having at least 5 carbon atoms per molecule and usable directly as fuels.

La zone de distillation comprend généralement au moins une colonne munie d'au moins un interne de distillation choisi dans le groupe formé par les plateaux, les garnissages en vrac et les garnissages structurés, ainsi qu'il est connu de l'homme du métier, de telle sorte que l'efficacité globale totale est au moins égale à cinq étages théoriques. Dans les cas connus de l'homme du métier où la mise en oeuvre d'une seule colonne peut poser des problèmes, on préfère alors scinder ladite zone de façon à utiliser finalement au moins deux colonnes qui, mises bout à bout, réalisent ladite zone.The distillation zone generally comprises at least one column provided with at least minus one internal distillation chosen from the group formed by the trays, the bulk packings and structured packings, as is known to those skilled in the art profession, so that the total overall efficiency is at least equal to five floors theoretical. In cases known to those skilled in the art where the implementation of a single column can cause problems, so we prefer to split the said zone so as to finally use at least two columns which, put together, achieve said area.

La charge de la zone de distillation est introduite à au moins un niveau d'introduction situé en-dessous du niveau de soutirage du liquide vers la zone réactionnelle, généralement à un niveau de 2 à 40 plateaux théoriques et de préférence de 2 à 20 plateaux théoriques en-dessous du niveau de soutirage du liquide vers ladite zone réactionnelle, ledit niveau de soutirage considéré étant le plus bas.The charge of the distillation zone is introduced at at least one introduction level located below the level of withdrawal of the liquid towards the reaction zone, generally at a level of 2 to 40 theoretical platforms and preferably from 2 to 20 theoretical plates below the level of withdrawal of the liquid towards said zone reaction, said withdrawal level considered being the lowest.

La zone réactionnelle comprend généralement au moins un lit catalytique, de préférence de 1 à 4 lit(s) catalytique(s) ; dans le cas où au moins deux lits catalytiques se trouvent incorporés dans la zone de distillation, ces deux lits sont éventuellement séparés par au moins un interne de distillation. The reaction zone generally comprises at least one catalytic bed, of preferably from 1 to 4 catalytic bed (s); if at least two beds are incorporated in the distillation zone, these two beds are optionally separated by at least one internal distillation.

Dans l'application particulière du procédé selon l'invention à la réduction sélective de la teneur en composés insaturés légers, comportant des oléfines éventuelles et du benzène d'une coupe d'hydrocarbures, la zone réactionnelle est une zone d'hydrogénation. Dans ce cas, la zone réactionnelle d'hydrogénation réalise au moins partiellement l'hydrogénation du benzène présent dans la charge, généralement de telle façon que la teneur en benzène du distillat liquide stabilisé soutiré au-dessous du niveau de prélèvement du distillat de tête soit au maximum égale à une certaine teneur, et ladite zone réactionnelle réalise au moins en partie, de préférence en majeure partie, l'hydrogénation de tout composé insaturé comprenant au plus six atomes de carbone par molécule et différent du benzène, éventuellement présent dans la charge.In the particular application of the method according to the invention to the selective reduction of the content of light unsaturated compounds, comprising possible olefins and benzene from a hydrocarbon fraction, the reaction zone is a zone hydrogenation. In this case, the hydrogenation reaction zone performs at least partially the hydrogenation of the benzene present in the feed, generally of so that the benzene content of the stabilized liquid distillate drawn off below the level of extraction of the top distillate is at most equal to a certain content, and said reaction zone performs at least in part, preferably in major part, the hydrogenation of any unsaturated compound comprising at most six carbon atoms per molecule and different from benzene, possibly present in charge.

La zone réactionnelle est au moins en partie externe à la zone de distillation. Généralement, le procédé selon l'invention comprend de 1 à 6, de préférence de 1 à 4 niveau(x) de prélèvement qui alimente(nt) la partie externe de la zone. Une partie de la partie externe de la zone réactionnelle qui est alimentée par un niveau de prélèvement donné, si la partie externe de la zone réactionnelle comprend au moins deux niveaux de prélèvement, comprend généralement au moins un réacteur, de préférence un seul réacteur.The reaction zone is at least partially external to the distillation zone. Generally, the method according to the invention comprises from 1 to 6, preferably from 1 to 4 level (s) of sampling which feed (s) the external part of the zone. A part of the external part of the reaction zone which is fed by a level of given sample, if the external part of the reaction zone comprises at least two levels of sampling, generally includes at least one reactor, preferably only one reactor.

Le niveau de réintroduction de la charge convertie au moins en partie dans la zone externe de réaction est généralement situé sensiblement au-dessous, ou sensiblement au-dessus, ou sensiblement à la même hauteur, d'au moins un niveau de prélèvement, de préférence dudit niveau de prélèvement de la charge de la zone de distillation. De manière préférée, le niveau de réintroduction est situé au-dessus du niveau de prélèvement.The level of reintroduction of the converted charge at least partly in the zone external reaction is usually located substantially below, or substantially above, or substantially at the same height, at least one level of sampling, preferably of said level of sampling of the load of the zone distillation. Preferably, the reintroduction level is located above the levy level.

Le réacteur étant au moins en partie externe, on prélève de la colonne un débit de liquide égal, supérieur ou inférieur au trafic liquide de la zone de distillation située en-dessous du niveau de soutirage de la charge à convertir.The reactor being at least partially external, a flow rate of liquid equal to, greater than or less than the liquid traffic of the distillation zone situated below the drawdown level of the load to be converted.

Dans l'application particulière de la conversion d'une charge de la zone de distillation à teneur en benzène plutôt élevée, par exemple à une teneur supérieure à environ 3 % en poids, le débit de liquide prélevé est de préférence égal ou supérieur au trafic liquide de la zone de distillation située en-dessous du niveau de soutirage.In the particular application of the conversion of a charge from the distillation zone with a rather high benzene content, for example at a content higher than approximately 3% by weight, the flow rate of liquid withdrawn is preferably equal to or greater than the traffic liquid from the distillation zone located below the draw-off level.

Dans l'application particulière de la conversion de charges à teneur en benzène plutôt faible par exemple à une teneur inférieure à environ 3 % en volume, le débit de liquide prélevé est de préférence égal ou inférieur au trafic liquide de la zone de distillation située en-dessous du niveau de soutirage.In the particular application of the conversion of charges with benzene content rather low for example at a content of less than about 3% by volume, the flow of liquid collected is preferably equal to or less than the liquid traffic in the area of distillation located below the racking level.

Le procédé selon l'invention permet de convertir une grande partie du (ou des) composé(s) à convertir à l'extérieur de la zone de distillation éventuellement dans des conditions de pression et/ou de température différentes de celles utilisées dans la zone de distillation.The method according to the invention makes it possible to convert a large part of (or) compound (s) to be converted outside the distillation zone possibly in pressure and / or temperature conditions different from those used in the distillation zone.

Le procédé selon l'invention est tel que l'écoulement du liquide à convertir est généralement co-courant à l'écoulement du flux gazeux comprenant de l'hydrogène, pour tout lit catalytique de la partie externe de la zone réactionnelle.The process according to the invention is such that the flow of the liquid to be converted is generally co-current to the flow of the gas stream comprising hydrogen, for any catalytic bed in the external part of the reaction zone.

Selon un mode de réalisation préféré du procédé selon l'invention, la zone réactionnelle est en totalité externe à la zone de distillation. Dans le cas où la partie externe de la zone réactionnelle comporte au moins deux lits catalytiques, chaque lit catalytique est alimenté par un seul niveau de prélèvement, de préférence associé à un seul niveau de réintroduction, ledit niveau de prélèvement étant distinct du niveau de prélèvement qui alimente l'(es) autre(s) lit(s) catalytique(s).According to a preferred embodiment of the method according to the invention, the area completely outside the distillation zone. In the event that the party external of the reaction zone comprises at least two catalytic beds, each bed catalytic is fed by a single level of sampling, preferably associated with a single level of reintroduction, said level of withdrawal being distinct from the level that feeds the other catalytic bed (s).

Selon un mode de réalisation préféré du procédé selon l'invention, la charge à convertir soutirée de la zone de distillation vers la zone réactionnelle est refroidie avant son entrée dans le réacteur. La charge convertie sortant du réacteur peut être refroidie avant sa réintroduction dans la zone de distillation. Ce refroidissement permet de créer un reflux circulant. De fait, au sens de la présente description, on désigne par reflux circulant, une circulation d'un liquide soutiré de la zone de distillation à un niveau et ré-introduit à un niveau au-dessus à une température inférieure à la température du liquide au niveau du soutirage.According to a preferred embodiment of the method according to the invention, the charge at convert withdrawn from the distillation zone to the reaction zone is cooled before entering the reactor. The converted charge leaving the reactor can be cooled before reintroduction into the distillation zone. This cooling creates a circulating reflux. In fact, within the meaning of the present description, we designates by circulating reflux, a circulation of a liquid withdrawn from the zone of distillation at one level and re-introduced at one level above at a temperature below the temperature of the liquid at the racking level.

Dans le cas particulier du procédé de réduction de la teneur en benzène d'une coupe d'hydrocarbures, un des modes de réalisation préférés de l'invention est tel que le niveau de réintroduction de la charge hydrogénée dans la colonne est situé au-dessus du niveau de prélèvement de la charge à hydrogéner dans une zone où la teneur en benzène est la plus faible. De manière encore plus préférée, le niveau de réintroduction est situé au moins 2 plateaux théoriques au-dessus du niveau de prélèvement et de manière encore plus préférée, le niveau de réintroduction de la charge est situé à au moins 4 plateaux théoriques au dessus du niveau de soutirage de ladite charge. In the particular case of the process for reducing the benzene content of a cut of hydrocarbons, one of the preferred embodiments of the invention is such that the level of reintroduction of the hydrogenated charge in the column is located above the level of withdrawal of the charge to be hydrogenated in an area where the Benzene content is the lowest. Even more preferably, the level of reintroduction is located at least 2 theoretical platforms above the level of even more preferably, the level of reintroduction of the load is located at least 4 theoretical platforms above the racking level of said charge.

Pour la réalisation de l'hydrogénation selon une application particulière du procédé de l'invention, le rapport molaire théorique d'hydrogène nécessaire pour la conversion désirée du benzène est de 3. La quantité d'hydrogène distribuée avant ou dans la zone d'hydrogénation est éventuellement en excès par rapport à cette stoechiométrie, et ce d'autant plus que l'on doit hydrogéner, en plus du benzène présent dans la charge, au moins partiellement tout composé insaturé comprenant au plus six atomes de carbone par molécule et présent dans ladite charge.For carrying out the hydrogenation according to a particular application of the process of the invention, the theoretical molar ratio of hydrogen necessary for the conversion desired benzene is 3. The amount of hydrogen distributed before or in the hydrogenation zone is possibly in excess with respect to this stoichiometry, and this all the more that one must hydrogenate, in addition to the benzene present in the filler, at least partially any unsaturated compound comprising at most six atoms of carbon per molecule and present in said charge.

De manière générale, l'hydrogène en excès, si il en existe, peut être avantageusement récupéré par exemple selon l'une des techniques décrites ci-après. Selon une première technique, l'hydrogène en excès qui sort de la zone réactionnelle est récupéré soit directement au niveau de l'effluent à la sortie de la zone réactionnelle, soit dans le distillat gazeux de la zone de distillation, puis comprimé et réutilisé dans ladite zone réactionnelle afin de créer un reflux. Selon une seconde technique, l'hydrogène en excès qui sort de la zone réactionnelle est récupéré, puis injecté en amont des étapes de compression associées à une unité de réformage catalytique, en mélange avec de l'hydrogène provenant de ladite unité, ladite unité opérant de préférence à basse pression, c'est-à-dire généralement une pression absolue inférieure à 0,8 MPa.In general, excess hydrogen, if any, can be advantageously recovered for example according to one of the techniques described below. According to a first technique, the excess hydrogen which leaves the reaction zone is recovered either directly at the effluent level at the exit of the zone reaction, either in the gaseous distillate of the distillation zone, then compressed and reused in said reaction zone in order to create a reflux. According to a second technique, the excess hydrogen which leaves the reaction zone is recovered, then injected upstream of the compression stages associated with a reforming unit catalytic, mixed with hydrogen from said unit, said unit preferably operating at low pressure, i.e. generally pressure absolute less than 0.8 MPa.

L'hydrogène, compris dans le flux gazeux, utilisé par exemple dans le procédé particulier de l'invention pour l'hydrogénation des composés insaturés comprenant au plus six atomes de carbone par molécule peut provenir de toutes sources produisant de l'hydrogène à au moins 50 % volume de pureté, de préférence au moins 80 % volume de pureté et de façon encore plus préférée au moins 90 % volume de pureté. Par exemple, on peut citer l'hydrogène provenant des procédés de réformage catalytique, de méthanation, de P.S.A. (adsorption par alternance de pression), de génération éléctrochimique ou de vapocraquage.Hydrogen, included in the gas flow, used for example in the process particular of the invention for the hydrogenation of unsaturated compounds comprising at least plus six carbon atoms per molecule can come from all sources producing hydrogen at least 50% purity volume, preferably at least 80% volume of purity and even more preferably at least 90% volume of purity. For example, mention may be made of hydrogen from reforming processes. catalytic, methanation, P.S.A. (alternating pressure adsorption), electrochemical or steam cracking generation.

Un des modes de réalisation préférés du procédé selon l'invention, indépendant ou non des modes de réalisation précédents, est tel que l'effluent de fond de la zone de distillation est mélangé au moins en partie au distillat liquide stabilisé récupéré à un niveau de récupération situé en-dessous du niveau de récupération du distillat vapeur. Dans le cas particulier du procédé de réduction de la teneur en benzène, le mélange ainsi obtenu peut être utilisé comme carburant soit directement, soit par incorporation aux fractions carburants. One of the preferred embodiments of the method according to the invention, independent or not from the previous embodiments, is such that the bottom effluent from the distillation is mixed at least in part with the stabilized liquid distillate recovered with a recovery level below the distillate recovery level steam. In the particular case of the process for reducing the benzene content, the mixture thus obtained can be used as fuel either directly or by incorporation into fuel fractions.

Lorsque la zone réactionnelle est en partie interne à la zone de distillation, les conditions opératoires de la partie de la zone réactionnelle interne à la zone de distillation sont liées aux conditions opératoires de la distillation. La distillation est réalisée sous une pression absolue généralement comprise entre 0,1MPa et 2,5 MPa avec un taux de reflux compris entre 0,1 et 20. La température de la zone de distillation est comprise entre 10 et 300°C. De manière générale, le liquide soumis à la conversion est mélangé à un flux gazeux comprenant de l'hydrogène dont le débit est au moins égal à la stoechiométrie des réactions de conversion réalisées et au plus égal au débit correspondant à 10 fois la stoechiométrie. Dans la partie externe de la zone réactionnelle, la catalyseur est disposé dans tout lit catalytique suivant toute technologie connue de l'homme du métier dans des conditions opératoires (température, pression...) indépendantes ou non, de préférence indépendantes, des conditions opératoires de la zone de distillation. Dans la partie de la zone réactionnelle externe à la zone de distillation, les conditions opératoires sont généralement les suivantes. La pression absolue requise est généralement comprise entre 0,1 et 6 MPa. La température opératoire est généralement comprise entre 30 et 400°C. La vitesse spatiale au sein de ladite zone réactionnelle, calculée par rapport au catalyseur, est généralement comprise entre 0,5 et 60 h-1. Le débit d'hydrogène correspondant à la stoechiométrie des réactions de conversion réalisées est compris entre 1 et 10 fois ladite stoechiométrie.When the reaction zone is partly internal to the distillation zone, the operating conditions of the part of the reaction zone internal to the zone of distillation are related to the operating conditions of the distillation. Distillation is performed under absolute pressure generally between 0.1MPa and 2.5 MPa with a reflux rate of between 0.1 and 20. The temperature of the distillation is between 10 and 300 ° C. In general, the liquid subjected to the conversion is mixed with a gas stream comprising hydrogen, the flow rate of which is at least equal to the stoichiometry of the conversion reactions carried out and at most equal to the flow corresponding to 10 times the stoichiometry. In the outer part of the reaction zone, the catalyst is placed in any catalytic bed following any technology known to those skilled in the art under operating conditions (temperature, pressure ...) independent or not, preferably independent, of operating conditions of the distillation zone. In the part of the area reaction external to the distillation zone, the operating conditions are usually the following. The absolute pressure required is generally understood between 0.1 and 6 MPa. The operating temperature is generally between 30 and 400 ° C. The space velocity within said reaction zone, calculated with respect to with the catalyst, is generally between 0.5 and 60 h-1. The flow of hydrogen corresponding to the stoichiometry of the conversion reactions carried out is understood between 1 and 10 times said stoichiometry.

Dans le cas particulier de l'hydrogénation du benzène et autres composés insaturés, les conditions opératoires sont les suivantes. Lorsque la zone d'hydrogénation est en partie interne à la zone de distillation, les conditions opératoires de la partie de la zone d'hydrogénation interne à la zone de distillation sont liées aux conditions opératoires de la distillation. La distillation est réalisée sous une pression absolue généralement comprise entre 0,2 et 2 MPa, de préférence entre 0,4 et 1 MPa, avec un taux de reflux compris entre 0,1 et 10, et de préférence compris entre 0,2 et 2. La température de tête de zone est comprise généralement entre 30 et 180°C et la température de fond de zone est comprise généralement entre 120 et 280°C. La réaction d'hydrogénation est conduite dans des conditions qui sont le plus généralement intermédiaires entre celles établies en tête et en fond de zone de distillation, à une température comprise entre 100 et 200°C, et de préférence comprise entre 120 et 180°C, et à une pression absolue comprise entre 0,2 et 3 MPa, de préférence entre 0,4 et 2 MPa. Le liquide soumis à l'hydrogénation est mélangé à un flux gazeux comprenant de l'hydrogène dont le débit dépend de la concentration en benzène dans ledit liquide et, plus généralement, des composés insaturés comportant au plus six atomes de carbone par molécule de la charge de la zone de distillation. Le débit d'hydrogène est généralement au moins égal au débit correspondant à la stoechiométrie des réactions d'hydrogénation réalisées (hydrogénation du benzène et des autres composés insaturés comportant au plus six atomes de carbone par molécule, compris dans la charge d'hydrogénation) et au plus égal au débit correspondant à 10 fois la stoechiométrie, de préférence compris entre 1 et 6 fois la stoechiométrie, de manière encore plus préférée compris entre 1 et 3 fois la stoechiométrie. Dans la partie de la zone d'hydrogénation externe à la zone de distillation, les conditions opératoires sont généralement les suivantes. La pression absolue requise pour cette étape d'hydrogénation est généralement comprise entre 0,1 et 6 MPa absolus, de préférence entre 0,2 et 5 MPa et de façon encore plus préférée entre 0,5 et 3,5 MPa. La température de la zone d'hydrogénation est généralement comprise entre 100 et 400 °C, de préférence entre 120 et 350 °C et de façon préférée entre 140 et 320 °C. La vitesse spatiale au sein de ladite zone d'hydrogénation, calculée par rapport au catalyseur, est généralement comprise entre 1 et 60 et plus particulièrement entre 1 et 40 h-1 (débit volumique de charge par volume de catalyseur). Le débit d'hydrogène correspondant à la stoechiométrie des réactions d'hydrogénation réalisées est compris entre 1 et 10 fois ladite stoechiométrie, de préférence entre 1 et 6 fois ladite stoechiométrie et de façon encore plus préférée entre 1 et 3 fois ladite stoechiométrie. Mais les conditions de température et de pression peuvent aussi, dans le cadre du procédé de la présente invention, être comprises entre celles qui sont établies en tête et en fond de zone de distillation.In the particular case of the hydrogenation of benzene and other unsaturated compounds, the operating conditions are as follows. When the hydrogenation zone is partly internal to the distillation zone, the operating conditions of the part of the hydrogenation zone internal to the distillation zone are linked to the operating conditions of the distillation. The distillation is carried out under an absolute pressure generally between 0.2 and 2 MPa, preferably between 0.4 and 1 MPa, with a reflux rate between 0.1 and 10, and preferably between 0.2 and 2. The zone head temperature is generally between 30 and 180 ° C and the zone bottom temperature is generally between 120 and 280 ° C. The hydrogenation reaction is carried out under conditions which are most generally intermediate between those established at the head and at the bottom of the distillation zone, at a temperature between 100 and 200 ° C., and preferably between 120 and 180 ° C. , and at an absolute pressure of between 0.2 and 3 MPa, preferably between 0.4 and 2 MPa. The liquid subjected to hydrogenation is mixed with a gas stream comprising hydrogen, the flow rate of which depends on the concentration of benzene in said liquid and, more generally, unsaturated compounds containing at most six carbon atoms per molecule of the charge. from the distillation zone. The hydrogen flow rate is generally at least equal to the flow rate corresponding to the stoichiometry of the hydrogenation reactions carried out (hydrogenation of benzene and of the other unsaturated compounds containing at most six carbon atoms per molecule, included in the hydrogenation charge) and at most equal to the flow rate corresponding to 10 times the stoichiometry, preferably between 1 and 6 times the stoichiometry, even more preferably between 1 and 3 times the stoichiometry. In the part of the hydrogenation zone external to the distillation zone, the operating conditions are generally as follows. The absolute pressure required for this hydrogenation step is generally between 0.1 and 6 MPa absolute, preferably between 0.2 and 5 MPa and even more preferably between 0.5 and 3.5 MPa. The temperature of the hydrogenation zone is generally between 100 and 400 ° C, preferably between 120 and 350 ° C and preferably between 140 and 320 ° C. The space velocity within said hydrogenation zone, calculated with respect to the catalyst, is generally between 1 and 60 and more particularly between 1 and 40 h -1 (volume flow rate of charge per volume of catalyst). The hydrogen flow rate corresponding to the stoichiometry of the hydrogenation reactions carried out is between 1 and 10 times said stoichiometry, preferably between 1 and 6 times said stoichiometry and even more preferably between 1 and 3 times said stoichiometry. However, the temperature and pressure conditions can also, within the scope of the process of the present invention, be between those which are established at the top and at the bottom of the distillation zone.

Au sens de la présente description, on désigne par taux de reflux, le rapport du débit massique du reflux sur le débit massique d'alimentation de la colonne.Within the meaning of the present description, the rate of reflux means the ratio of the flow mass of the reflux on the mass flow rate of the column.

Dans le cas particulier où la zone réactionnelle est une zone d'hydrogénation du benzène et éventuellement des oléfines, le catalyseur utilisé dans la zone d'hydrogénation comprend généralement au moins un métal choisi dans le groupe VIII, choisi de préférence dans le groupe formé par le nickel et le platine, utilisé tel quel ou de préférence déposé sur un support. Le métal doit généralement se trouver sous forme réduite au moins pour 50 % en poids de sa totalité. Mais tout autre catalyseur d'hydrogénation connu de l'homme du métier peut également être choisi.In the particular case where the reaction zone is a hydrogenation zone of the benzene and possibly olefins, the catalyst used in the area hydrogenation generally comprises at least one metal chosen from the group VIII, preferably chosen from the group formed by nickel and platinum, used as such which or preferably deposited on a support. The metal should generally be found in reduced form at least for 50% by weight of its totality. But any other hydrogenation catalyst known to those skilled in the art can also be chosen.

Dans le cas de l'utilisation du nickel, la proportion de nickel par rapport au poids total de catalyseur est comprise entre 5 et 70 %, plus particulièrement entre 10 et 70 % et de façon préférée entre 15 et 65 %. De plus, on utilise généralement un catalyseur tel que la taille moyenne des cristallites de nickel est inférieure à 100.10 -10 m, de préférence inférieure à 80.10-10 m, de façon encore plus préférée inférieure à 60.10 -10m.In the case of the use of nickel, the proportion of nickel relative to the total weight of catalyst is between 5 and 70%, more particularly between 10 and 70% and preferably between 15 and 65%. In addition, a catalyst is generally used such that the average size of the nickel crystallites is less than 100.10 -10 m, preferably less than 80.10 -10 m, even more preferably less than 60.10 -10 m.

Le support est généralement choisi dans le groupe formé par l'alumine, les silice-alumines, la silice, les zéolithes, le charbon actif, les argiles, les ciments alumineux, les oxydes de terres rares et les oxydes alcalino-terreux, seuls ou en mélange. On utilise de préférence un support à base d'alumine ou de silice, de surface spécifique comprise entre 30 et 300 m2/g, de préférence entre 90 et 260 m2/g.The support is generally chosen from the group formed by alumina, silica-aluminas, silica, zeolites, activated carbon, clays, aluminous cements, rare earth oxides and alkaline earth oxides, alone or in mixture. A support based on alumina or silica is preferably used, with a specific surface area of between 30 and 300 m 2 / g, preferably between 90 and 260 m 2 / g.

La figure 1 est une illustration d'une possibilité de réalisation du procédé selon l'invention.Figure 1 is an illustration of a possibility of carrying out the method according to the invention.

La charge d'hydrocarbures est envoyée dans une colonne 2 par la ligne 1. Ladite colonne contient des internes de distillation, qui sont par exemple dans le cas représenté sur la figure 1 des plateaux ou du garnissage, représentés en partie par des traits pointillés sur ladite figure.The hydrocarbon charge is sent to column 2 by line 1. Said column contains internal distillation, which is for example in the case represented in FIG. 1 of the plates or of the lining, represented in part by dotted lines in said figure.

En pied de colonne, la fraction la moins volatile du réformat est récupérée par la ligne 5, une partie est rebouillie dans l'échangeur 6 et une partie est évacuée par la ligne 7. La vapeur de rebouillage est réintroduite dans la colonne par la ligne 8. Le distillat liquide stabilisé est extrait par la ligne 18, le distillat vapeur est envoyé par la ligne 9 dans un condenseur 10 puis dans un ballon 11 d'où le distillat vapeur est extrait par la ligne 14 . La phase liquide du ballon 11 est renvoyée pour partie, par la ligne 12, en tête de colonne pour en assurer le reflux, et une autre partie de la phase liquide peut être récupérée par la ligne 13.At the bottom of the column, the least volatile fraction of the reformate is recovered by the line 5, a part is reboiled in the exchanger 6 and a part is evacuated via line 7. Reboiling steam is reintroduced into the column by line 8. The distillate stabilized liquid is extracted by line 18, the steam distillate is sent by line 9 in a condenser 10 then in a flask 11 from which the steam distillate is extracted by the line 14. The liquid phase of the balloon 11 is partially returned via line 12, in column head to reflux, and another part of the liquid phase can be picked up by line 13.

Au moyen d'un plateau de soutirage disposé dans la zone de distillation, on soutire par la ligne 15 un liquide que l'on envoie en tête d'un réacteur 3, après adjonction d'hydrogène par la ligne 4. L'effluent du réacteur est refroidi dans l'échangeur 16 puis recyclé à la colonne par la ligne 17. By means of a racking plate placed in the distillation zone, it is racked via line 15 a liquid which is sent to the head of a reactor 3, after addition of hydrogen via line 4. The reactor effluent is cooled in exchanger 16 then recycled to the column by line 17.

L'effluent liquide à séparer est soutiré de la zone de distillation par la ligne 19, puis envoyé dans une zone de séparation latérale gaz-liquide (20), d'où on recycle l'effluent gazeux dans la zone de distillation par la ligne 21 et on récupère une coupe intermédiaire par la ligne 23, une partie de la coupe est rebouillie dans l'échangeur 22.The liquid effluent to be separated is withdrawn from the distillation zone by line 19, then sent to a gas-liquid side separation zone (20), from which it is recycled the gaseous effluent in the distillation zone via line 21 and a section is recovered intermediate through line 23, part of the section is rewashed in the exchanger 22.

EXEMPLE (selon l'invention)EXAMPLE (according to the invention)

L' exemple qui suit illustre une application particulière de l'invention, c'est-à-dire la réduction sélective en composés insaturés et en benzène d'une coupe d'hydrocarbures. Ils sont réalisés par simulation numérique à l'aide du logiciel PRO/II® de la société Simulation Sciences Incorporated.The example which follows illustrates a particular application of the invention, that is to say the selective reduction of unsaturated compounds and benzene from a cut of hydrocarbons. They are carried out by digital simulation using software PRO / II® from Simulation Sciences Incorporated.

Le procédé possède une configuration avec soutirage d'un effluent liquide vers une zone de séparation latérale gaz-liquide, avec réintroduction de l'effluent gazeux dans la zone de distillation et récupération de l'effluent liquide comme coupe intermédiaire. L'unité est représentée sur la figure 1.The process has a configuration with withdrawal of a liquid effluent to a lateral gas-liquid separation zone, with reintroduction of the gaseous effluent into the distillation and recovery zone of the liquid effluent as an intermediate cut. The unit is shown in Figure 1.

Le procédé possède une configuration avec soutirage d'un effluent liquide stabilisé en dessous du soutirage d'un distillat vapeur et avec un niveau de réintroduction de la charge hydrogénée 9 plateaux au dessus du plateau de soutirage.The process has a configuration with withdrawal of a liquid effluent stabilized in below the racking of a steam distillate and with a level of reintroduction of the hydrogenated charge 9 trays above the racking tray.

La colonne comprend 57 plateaux théoriques (y compris condenseur et rebouilleur) et possède un diamètre de 3,35 m.
La colonne latérale associée comporte 7 plateaux théoriques (y compris le rebouilleur).
Le taux de reflux par rapport à l'alimentation (exprimé en poids ) est de 1,02. La puissance de rebouillage est de 12800 kW. La puissance du rebouilleur de la colonne latérale est de 271 kW.The column includes 57 theoretical plates (including condenser and reboiler) and has a diameter of 3.35 m.
The associated side column has 7 theoretical plates (including the reboiler).
The reflux rate relative to food (expressed by weight) is 1.02. The reboiling power is 12800 kW. The power of the side column reboiler is 271 kW.

Le procédé est mis en oeuvre avec un réacteur d'hydrogénation externe contenant 7 m3 de catalyseur et fonctionnant à une pression absolue de 1,5 MPa. Le catalyseur au nickel est vendu par la société PROCATALYSE sous la référence LD746.The process is carried out with an external hydrogenation reactor containing 7 m 3 of catalyst and operating at an absolute pressure of 1.5 MPa. The nickel catalyst is sold by the company PROCATALYSE under the reference LD746.

On récupère l'effluent liquide stabilisé (réformat léger) au plateau 3 par la ligne 18 et le distillat vapeur en tête de colonne par la ligne 14. La charge pour la colonne est injectée par la ligne 1 au plateau 37. La charge pour le réacteur 3 est soutirée du plateau 30 via la ligne 15. L'hydrogène est introduit par la ligne 4 avant d'entrer dans le réacteur fonctionnant en écoulement descendant et sous 1,5 MPa de pression absolue. Le rapport molaire hydrogène/benzène est de 2,63. L'effluent du réacteur 3 est refroidi puis ré-injecté dans la colonne via la ligne 17 au plateau 21. La pression absolue au ballon de reflux est de 0,75 MPa.The stabilized liquid effluent is recovered (light reformate) at plate 3 via line 18 and the steam distillate at the top of the column via line 14. The charge for the column is injected by line 1 into plate 37. The charge for reactor 3 is withdrawn from tray 30 via line 15. Hydrogen is introduced via line 4 before entering the reactor operating in downflow and at 1.5 MPa pressure absolute. The hydrogen / benzene molar ratio is 2.63. The effluent from reactor 3 is cooled and then re-injected into the column via line 17 on plate 21. The pressure absolute at the reflux flask is 0.75 MPa.

Les compositions simulées des fractions de liquide stabilisé (réformat léger) (18), vapeur de purge (14), réformat lourd (7) et coupe intermédiaire (23) sont indiquées dans le tableau 1.Simulated compositions of stabilized liquid fractions (light reformate) (18), purge steam (14), heavy reformate (7) and intermediate cut (23) are indicated in table 1.

On constate que le procédé selon la présente invention, où il y a soutirage d'un distillat liquide traité dans une zone de séparation latérale permet de récupérer une coupe intermédiaire directement utilisable. Dans cet exemple particulier, la coupe intermédiaire est une coupe naphta comprenant environ 3,8% volume de benzène.It is found that the method according to the present invention, where there is withdrawal of a liquid distillate treated in a lateral separation zone makes it possible to recover a directly usable intermediate cut. In this particular example, the cut intermediate is a naphtha cut comprising approximately 3.8% by volume of benzene.

Le reformat léger (18) contient 0,35 % volume de benzène, le reformat lourd (7) contient
0,6 % volume de benzène. La tension de vapeur REID du naphta est de 0,086 MPa, et celle du mélange constitué par le reformat léger et le reformat lourd est de 0,022 MPa. Composition de la charge et des effluents pour l'exemple 1 (cas soutirage latérale ) Corps/ kmoles/h charge H2 Purge Vapeur (14) Réformat Léger (18) soutirage naphta (23) Réformat Lourd (7) H2 0,00 183,13 5,03 0,00 0,00 0,00 methane 0,00 31,85 31,84 0,02 0,00 0,00 ethane 0,00 15,63 15,55 0,08 0,00 0,00 propane 0,00 6,64 6,20 0,45 0,00 0,00 butanes 13,63 0,84 8,40 5,85 0,21 0,00 iso pentanes 60,80 0,25 5,96 52,40 2,70 0,00 normal pentanes 43,33 0,11 2,49 38,81 2,60 0,00 diméthylbutanes 15,88 0,14 11,04 4,71 0,00 autres paraffines C6 62,87 0,16 23,59 39,13 0,00 hexane 31,92 0,00 1,19 33,52 0,01 paraffines C7 53,60 0,00 0,00 20,70 33,20 paraffines C8 6,93 0,00 0,00 0,01 6,93 paraffines C9+ 2,96 0,00 0,00 0,00 2,96 cyclopentane 2,74 0,05 2,34 0,35 0,00 méthylcyclopentane 4,47 0,00 0,03 4,39 0,04 cyclohexane 0,45 0,00 0,01 44,87 9,02 méthylcyclohexane 3,67 0,00 0,00 1,47 6,92 naphtènes C8 0,50 0,00 0,00 0,00 0,50 pentènes 1,17 0,07 0,58 0,05 0,00 hexènes 2,99 0,00 0,01 0,17 0,00 heptènes 1,50 0,00 0,00 0,03 1,16 benzène 69,45 0,00 0,65 8,58 6,77 toluène 286,57 0,00 0,00 0,31 281,53 aromatiques C8 307,41 0,00 0,00 0,03 307,38 aromatiques C9+ 165,13 0,00 0,00 0,00 165,13 TOTAL 1137,96 238,46 75,87 137,05 163,84 821,55 The light reformate (18) contains 0.35% by volume of benzene, the heavy reformate (7) contains
0.6% volume of benzene. The REID vapor pressure of naphtha is 0.086 MPa, and that of the mixture constituted by the light reformate and the heavy reformate is 0.022 MPa. Composition of the feed and effluents for example 1 (case of lateral withdrawal) Body / kmoles / h charge H2 Steam Purge (14) Light Reform (18) naphtha filling (23) Heavy Reformat (7) H2 0.00 183.13 5.03 0.00 0.00 0.00 methane 0.00 31.85 31.84 0.02 0.00 0.00 ethane 0.00 15.63 15.55 0.08 0.00 0.00 propane 0.00 6.64 6.20 0.45 0.00 0.00 butanes 13.63 0.84 8.40 5.85 0.21 0.00 iso pentanes 60.80 0.25 5.96 52.40 2.70 0.00 normal pentanes 43.33 0.11 2.49 38.81 2.60 0.00 dimethylbutanes 15.88 0.14 11.04 4.71 0.00 other C6 paraffins 62.87 0.16 23.59 39.13 0.00 hexane 31.92 0.00 1.19 33.52 0.01 C7 paraffins 53.60 0.00 0.00 20.70 33.20 C8 paraffins 6.93 0.00 0.00 0.01 6.93 C9 + paraffins 2.96 0.00 0.00 0.00 2.96 cyclopentane 2.74 0.05 2.34 0.35 0.00 methylcyclopentane 4.47 0.00 0.03 4.39 0.04 cyclohexane 0.45 0.00 0.01 44.87 9.02 methylcyclohexane 3.67 0.00 0.00 1.47 6.92 naphthenes C8 0.50 0.00 0.00 0.00 0.50 pentenes 1.17 0.07 0.58 0.05 0.00 hexenes 2.99 0.00 0.01 0.17 0.00 heptenes 1.50 0.00 0.00 0.03 1.16 benzene 69.45 0.00 0.65 8.58 6.77 toluene 286.57 0.00 0.00 0.31 281.53 aromatics C8 307.41 0.00 0.00 0.03 307.38 aromatic C9 + 165.13 0.00 0.00 0.00 165.13 TOTAL 1,137.96 238.46 75.87 137.05 163.84 821.55

Claims (16)

Procédé de conversion d'une charge d'hydrocarbures, tel que l'on traite ladite charge dans une zone de distillation produisant un distillat en tête et un effluent de fond, associée à une zone réactionnelle au moins en partie externe, comprenant au moins un lit catalytique, dans laquelle on réalise au moins une réaction de conversion d'au moins une partie d'au moins un hydrocarbure, en présence d'un catalyseur et d'un flux gazeux comprenant de l'hydrogène, la charge de la zone réactionnelle étant prélevée à la hauteur d'au moins un niveau de prélèvement et représentant au moins une partie du liquide coulant dans la zone de distillation, l'effluent de la zone réactionnelle étant au moins en partie réintroduit dans la zone de distillation à la hauteur d'au moins un niveau de réintroduction, de manière à assurer la continuité de la distillation, ledit procédé étant caractérisé en ce qu'on soutire de la zone de distillation un effluent liquide à la hauteur d'au moins un niveau de soutirage, au moins une partie dudit effluent liquide étant au moins en partie traitée dans une zone de séparation latérale gaz-liquide (splitter), dont l'effluent gazeux est au moins en partie réintroduit dans la zone de distillation et dont l'effluent liquide est au moins en partie récupéré comme coupe intermédiaire.Method for converting a hydrocarbon charge, as treated charge in a distillation zone producing a distillate at the top and an effluent from bottom, associated with a reaction zone at least partly external, comprising at least at least one catalytic bed, in which at least one conversion reaction is carried out at least part of at least one hydrocarbon, in the presence of a catalyst and of a gas stream comprising hydrogen, the charge of the reaction zone being sampled at the level of at least one level of sampling and representing at least part of the liquid flowing in the distillation zone, the effluent from the zone reaction being at least partly reintroduced into the distillation zone at the height of at least one reintroduction level, so as to ensure continuity of distillation, said process being characterized in that it is withdrawn from the distillation of a liquid effluent up to at least one racking level, at at least part of said liquid effluent being at least partly treated in an area gas-liquid side separation (splitter), the gaseous effluent of which is at least part reintroduced into the distillation zone and whose liquid effluent is at least in part recovered as an intermediate cut. Procédé selon la revendication 1 comprenant un seul niveau de soutirage de l'effluent liquide vers la zone de séparation latérale gaz-liquide.The method of claim 1 comprising a single level of withdrawal of the liquid effluent to the lateral gas-liquid separation zone. Procédé selon l'une des revendications 1 et 2 dans on soutire en outre un distillat liquide stabilisé à un niveau de prélèvement situé en dessous du niveau du distillat vapeur.Process according to either of Claims 1 and 2, in which a distillate is also drawn off liquid stabilized at a sampling level located below the distillate level steam. Procédé selon l'une des revendications 1 à 3 comprenant un seul niveau de prélèvement de la charge de la zone réactionnelle.Method according to one of claims 1 to 3 comprising a single level of charge taken from the reaction zone. Procédé selon l'une des revendications 1 à 4 dans lequel le niveau de réintroduction de l'effluent de la zone réactionnelle est situé au-dessus du niveau de prélèvement de la charge de la zone réactionnelle.Method according to one of Claims 1 to 4, in which the level of reintroduction of the reaction zone effluent is located above the level of charge taken from the reaction zone. Procédé selon la revendication 5 dans lequel le niveau de réintroduction de l'effluent de la zone réactionnelle est au moins le deuxième plateau théorique au-dessus du niveau de prélèvement de la charge de la zone réactionnelle. The method of claim 5 wherein the level of reintroduction of the reaction zone effluent is at least the second theoretical plateau above the level of withdrawal of the charge from the reaction zone. Procédé selon l'une des revendications 1 à 6 dans lequel la zone réactionnelle est en totalité externe à la zone de distillation.Process according to one of Claims 1 to 6, in which the reaction zone is entirely external to the distillation zone. Procédé selon l'une des revendications 1 à 7 tel que la distillation est réalisée sous une pression absolue comprise entre 0,1 et 2,5 MPa, avec un taux de reflux compris entre 0,1 et 20 et à une température comprise entre 10 et 300°C.Process according to one of Claims 1 to 7, such that the distillation is carried out under an absolute pressure between 0.1 and 2.5 MPa, with a reflux rate included between 0.1 and 20 and at a temperature between 10 and 300 ° C. Procédé selon l'une des revendications 1 à 8 tel que, pour la partie de la réaction de conversion externe à la zone de distillation, la pression absolue est comprise entre 0,1 et 6 MPa, la température est comprise entre 30 et 400°C, la vitesse spatiale au sein de la zone de conversion, calculée par rapport au catalyseur, est comprise entre 0,5 et 60 h-1 (volume de charge par volume de catalyseur et par heure), et le débit d'hydrogène est compris entre une et 10 fois le débit correspondant à la stoechiométrie des réactions de conversion mises en jeu.Method according to one of claims 1 to 8 such that, for the part of the conversion reaction external to the distillation zone, the absolute pressure is between 0.1 and 6 MPa, the temperature is between 30 and 400 ° C, the space speed within the conversion zone, calculated relative to the catalyst, is between 0.5 and 60 h -1 (volume of charge per volume of catalyst and per hour), and the hydrogen flow rate is between one and 10 times the flow rate corresponding to the stoichiometry of the conversion reactions involved. Procédé selon l'une des revendications 1 à 9 tel que l'on traite une charge constituée en majeure partie par des hydrocarbures comportant au moins 5 atomes de carbone par molécule et comprenant au moins un composé insaturé, comportant au moins une oléfine éventuelle et du benzène.Method according to one of claims 1 to 9 as treating a load consisting mainly of hydrocarbons containing at least 5 atoms of carbon per molecule and comprising at least one unsaturated compound, comprising at least one optional olefin and benzene. Procédé selon la revendication 10 tel que la zone réactionnelle est une zone d'hydrogénation, dans laquelle on réalise l'hydrogénation d'au moins une partie des composés insaturés comprenant au plus six atomes de carbone par molécule et contenus dans la charge, en présence d'un catalyseur d'hydrogénation.Process according to claim 10 such that the reaction zone is a zone of hydrogenation, in which the hydrogenation of at least part of the unsaturated compounds containing at most six carbon atoms per molecule and contained in the feed, in the presence of a hydrogenation catalyst. Procédé selon l'une des revendications 10 à 11 tel que l'effluent liquide issu de la zone de de séparation latérale gaz-liquide représente une coupe intermédiaire comprenant moins de 5% poids de benzène.Method according to one of claims 10 to 11 such as the liquid effluent from the gas-liquid side separation zone represents an intermediate section comprising less than 5% by weight of benzene. Procédé selon l'une des revendications 10 à 12 tel que la distillation est réalisée sous une pression absolue comprise entre 0,2 et 2 MPa, avec un taux de reflux compris entre 0,1 et 10, la température de tête de zone de distillation étant comprise entre 30 et 180°C et la température de fond de zone de distillation étant comprise entre 120 et 280°C.Method according to one of claims 10 to 12 as the distillation is carried out under an absolute pressure between 0.2 and 2 MPa, with a reflux rate between 0.1 and 10, the head temperature of the distillation zone being between between 30 and 180 ° C and the bottom temperature of the distillation zone being included between 120 and 280 ° C. Procédé selon l'une des revendications 10 à 13 tel que, pour la partie de la réaction d'hydrogénation externe à la zone de distillation, la pression absolue est comprise entre 0,1 et 6 MPa, la température est comprise entre 100 et 400°C, la vitesse spatiale au sein de la zone d'hydrogénation, calculée par rapport au catalyseur, est comprise entre 1 et 60 h-1 (volume de charge par volume de catalyseur et par heure), et le débit d'hydrogène est compris entre une et 10 fois le débit correspondant à la stoechiométrie des réactions d'hydrogénation mises en jeu.Method according to one of claims 10 to 13 such that, for the part of the hydrogenation reaction external to the distillation zone, the absolute pressure is between 0.1 and 6 MPa, the temperature is between 100 and 400 ° C, the space speed within the hydrogenation zone, calculated with respect to the catalyst, is between 1 and 60 h -1 (volume of charge per volume of catalyst and per hour), and the hydrogen flow rate is between one and 10 times the flow rate corresponding to the stoichiometry of the hydrogenation reactions involved. Procédé selon l'une des revendications 10 à 14 tel que, pour la partie de la réaction d'hydrogénation interne à la zone de distillation, la réaction d'hydrogénation est conduite à une température comprise entre 100 et 200°C, à une pression absolue comprise entre 0,2 et 3 MPa, et le débit de l'hydrogène alimentant la zone d'hydrogénation est compris entre une fois et 10 fois le débit correspondant à la stoechiométrie des réactions d'hydrogénation mises en jeu.Method according to one of claims 10 to 14 such that, for the part of the internal hydrogenation reaction in the distillation zone, the hydrogenation reaction is conducted at a temperature between 100 and 200 ° C, at an absolute pressure between 0.2 and 3 MPa, and the flow rate of hydrogen supplying the area hydrogenation is between once and 10 times the flow rate corresponding to the stoichiometry of the hydrogenation reactions involved. Procédé selon l'une des revendications 10 à 15 tel que le catalyseur utilisé dans la zone réactionnelle d'hydrogénation comprend au moins un métal choisi dans le groupe formé par le nickel et le platine.Process according to one of Claims 10 to 15, such as the catalyst used in the hydrogenation reaction zone comprises at least one metal chosen from the group formed by nickel and platinum.
EP99402025A 1998-08-17 1999-08-10 Hydrocarbon conversion process and its application in the hydrogenation of benzene Expired - Lifetime EP0980909B1 (en)

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