EP0949315A1 - Verfahren zur Umsetzung von Kohlenwasserstoffen durch Behandlung in einer mit einer Reaktionszone verbundenen Distillationsanlage und Anwendung fur die Hydrogeniering von Benzol - Google Patents

Verfahren zur Umsetzung von Kohlenwasserstoffen durch Behandlung in einer mit einer Reaktionszone verbundenen Distillationsanlage und Anwendung fur die Hydrogeniering von Benzol Download PDF

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EP0949315A1
EP0949315A1 EP99400738A EP99400738A EP0949315A1 EP 0949315 A1 EP0949315 A1 EP 0949315A1 EP 99400738 A EP99400738 A EP 99400738A EP 99400738 A EP99400738 A EP 99400738A EP 0949315 A1 EP0949315 A1 EP 0949315A1
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Prior art keywords
zone
level
hydrogenation
distillation
charge
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French (fr)
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EP0949315B1 (de
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Jean-Louis Ambrosino
Blaise Didillon
Pierre Marache
Jean-Charles Viltard
Gérald Witte
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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
    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
    • 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. So this process makes it possible to selectively convert hydrocarbons separated from a hydrocarbon charge thanks to the distillation zone.
  • the method according to the invention applies to the reduction selective for the content of light unsaturated compounds (i.e. containing at most six carbon atoms per molecule) containing possible olefins and benzene, of a fraction of hydrocarbons essentially comprising at least 5 carbon atoms per molecule, without significant loss of the octane number.
  • Benzene has carcinogenic properties and is therefore required to limit to the maximum any possibility of polluting the ambient air, in particular by excluding it practically automotive fuels. In the United States fuels reformulated 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 common hydrocarbons reagents in the photochemical reaction cycle with nitrogen oxides, which produced 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 treatment naphtha catalyst intended to produce aromatic hydrocarbons, mainly comprising from 6 to 9 carbon atoms in their molecule and whose very high octane number gives gasoline its knock properties.
  • the benzene in a reformate can be hydrogenated to cyclohexane.
  • benzene in a reformate can be hydrogenated to cyclohexane.
  • he is impossible to selectively hydrogenate benzene from a mixture of hydrocarbons also containing toluene and xylenes, therefore it is necessary to fractionate this mixture beforehand so as to isolate a section not containing than benzene, which can then be hydrogenated.
  • Patent application WO 95/15934 describes a reactive distillation which aims selectively hydrogenating diolefins and acetylenic compounds C2-C5.
  • the distillate can be recovered separately from the light ones.
  • the catalytic zone hydrogenation is completely internal to the distillation column, which does not not allow a good dissolution of hydrogen in the charge nor power increase the pressure.
  • the patent application of the applicant EP 0 781 830 A1 describes a process hydrogenation of benzene in which a distillation column is used associated with a reaction zone at least partly external.
  • the effluent is recovered at the head of the column, then by a condenser, arrives in a balloon from which a new separation operation is necessary to recover the desired product.
  • the column head effluent includes light gases such as that the excess hydrogen mixed with the reformate depleted in benzene and the distillate liquid contains a lot of dissolved gas which may require a step additional separation.
  • 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. combining a distillation zone producing a steam distillate and an effluent from bottom, and a reaction zone at least partially external to the distillation zone. At least one conversion reaction of at least part of at least one hydrocarbon takes place in a reaction zone comprising at least one bed catalytic, in the presence of a catalyst and a gas flow comprising hydrogen. The charge of the reaction zone is taken at the height of a level of sampling and represents at least part of the liquid flowing in the distillation zone, and the effluent from the reaction zone is at least partly reintroduced into the distillation zone at the level of at least one level of reintroduction, so as to ensure the continuity of the distillation.
  • the invention is characterized in that a liquid distillate is drawn from the distillation zone height of at least one racking level, said level being located below the draw-off level of said steam distillate.
  • liquid distillate is understood to mean a fraction liquid drawn from the distillation zone separate from the charge of the zone reactive.
  • the method according to the invention is characterized by the dissociation of the level of withdrawal of liquid distillate from the level of withdrawal of gaseous distillate, the liquid distillate being withdrawn at a recovery level below the level recovery of the steam distillate.
  • the product sought is recovered as stabilized liquid distillate, i.e. freed from most of excess hydrogen and possibly light gases.
  • this recovery separate steam distillate eliminates other gases by the gas distillate that the hydrogen present in the gas stream comprising mainly of the hydrogen introduced to carry out the conversion reaction.
  • the process according to the invention in its particular application, makes it possible to recover directly by drawing off from the distillation zone a stabilized liquid distillate in which the selective hydrogenation of benzene and of any compound has been carried out at least partially unsaturated 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 carbon atoms per molecule)
  • the method according to the invention is for example a method of treating a feed, consisting mainly of hydrocarbons comprising at least 5, preferably between 5 and 9 carbon atoms per molecule, and comprising at least at least one unsaturated compound, comprising optional olefins and benzene, as the said charge is treated in a distillation zone, associated with a zone hydrogenation reaction at least in external part, comprising at least a catalytic bed, in which the hydrogenation of at least part is carried out unsaturated compounds comprising at most six carbon atoms per molecule, that is to say comprising up to six (inclusive) carbon atoms per molecule, and contained in the feed, in the presence of a hydrogenation catalyst and a flow gaseous comprising, preferably for the most part, hydrogen, the charge of the reaction zone being sampled at the level of a sampling level and representing at least a part, preferably the major part, of the liquid flowing in the distillation zone, the effluent from the reaction zone being at less in part, preferably for
  • the liquid distillate recovered is stabilized. Indeed, the liquid distillate is drawn off at a level of sampling below the level of recovery of light gases containing excess hydrogen.
  • the light gases pass through a condenser then in a reflux flask from which at least part of the liquid fraction is recycled in the distillation zone and at least part of the liquid fraction can possibly be recovered.
  • the stabilized liquid distillate contains essentially liquid compounds having at least 5 carbon atoms and usable directly as fuels.
  • 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 the same height of at least one level of collection, preferably of said level of collection of the charge of the distillation zone.
  • the reintroduction level is located at the above the withdrawal level.
  • the recovery level of the stabilized liquid distillate is generally located above or below or at substantially the same height of at least one reintroduction level of the converted charge at least partly in the zone external reaction.
  • the level of recovery of the liquid distillate stabilized is located above at least one level of load removal from the distillation 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 known to man of the trade, such that the total overall efficiency is at least equal to five stages theoretical.
  • the total overall efficiency is at least equal to five stages theoretical.
  • the charge of the distillation zone is introduced at at least one level of introduction located below the level of withdrawal of the liquid towards the zone reactionary, generally at a level of 10 to 40 theoretical platforms and preferably 15 to 25 theoretical trays below the racking level of the liquid towards said reaction zone, said withdrawal level considered being the lower.
  • 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 at least partially the hydrogenation of the benzene present in the feed, generally such that the benzene content of the stabilized liquid distillate either at most equal to a certain content, and said reaction zone achieves at least in part, preferably in major part, the hydrogenation of all unsaturated compound comprising at most six carbon atoms per molecule and different from benzene, possibly present in the feed.
  • 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 at 4 level (s) of sampling which feed (s) the external part of the zone.
  • the reactor being at least partly external, a flow rate of liquid equal, superior or inferior to the liquid traffic of the distillation zone located below the draw-off level of the load to be converted.
  • the flow rate of liquid withdrawn is preferably equal to or greater than the liquid traffic of the distillation zone located below the racking level.
  • the flow rate of liquid withdrawn 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 under pressure and / or temperature conditions different from that 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 catalytic bed is supplied by a single level of sampling, preferably associated with a single level of reintroduction, said level of withdrawal being distinct from the level of sampling which feeds the other bed (s) catalytic (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.
  • circulating reflux means a circulation of a liquid withdrawn from the distillation zone to a level and re-introduced to a level above at a temperature lower than the temperature of the liquid at the racking level.
  • one of the preferred embodiments of the invention is such that the level of reintroduction of the hydrogenated charge into 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 plates above the level of even more preferably, the level of reintroduction of the charge is located at least 4 theoretical platforms above the level of withdrawal of said charge.
  • the preferred implementation described above makes it possible to greatly reduce the amount of catalyst required. Indeed, this implementation makes it possible to withdraw more liquid from the distillation area to convert a larger amount of benzene in the reactor without disturbing column traffic outside the area where it is withdrawn and without disturbing the profile column concentration. Reintroduction to a level above therefore makes it possible to greatly reduce the amount of catalyst necessary for obtain a quantity of benzene in the final effluent as low or even lower than in the processes according to the prior art.
  • this preferred embodiment of the invention generally makes it possible to reduce the reboiling power necessary for the continuity of the distillation.
  • the theoretical molar ratio of hydrogen necessary for the desired benzene conversion is 3.
  • the amount of hydrogen distributed before or in the hydrogenation zone is possibly in excess compared to this stoichiometry, and all the more that one must hydrogenate, in addition to benzene present in the filler, at least partially any unsaturated compound comprising at most six carbon atoms 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 zone reaction is recovered either directly at the level of the effluent at the outlet of the reaction zone, 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 steps associated with a unit catalytic reforming, in mixture with hydrogen coming from said unit, said unit preferably operating at low pressure, that is to say generally an absolute pressure of 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 most six carbon atoms per molecule can come from all sources producing hydrogen at least 50% by volume of purity, preferably at at least 80% purity volume and even more preferably at least 90% volume of purity.
  • hydrogen from processes catalytic reforming, methanation, P.S.A. (alternating adsorption of pressure), electrochemical generation or steam cracking.
  • One of the preferred embodiments of the method according to the invention is such that the bottom effluent from the zone at least partly mixed with the recovered stabilized liquid distillate at a recovery level below the recovery level of the steam distillate.
  • the mixture thus obtained can be used as fuel either directly, or by incorporation into the 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 an absolute pressure generally between 0.1 MPa and 2.5 MPa with a reflux rate between 0.1 and 20.
  • the temperature of the area distillation is between 10 and 300 ° C.
  • the liquid subjected to conversion is mixed with a gas stream comprising hydrogen whose flow rate is at least equal to the stoichiometry of the conversion reactions performed and at most equal to the flow rate corresponding to 10 times the stoichiometry.
  • the catalyst is placed in any bed catalytic according to any technology known to those skilled in the art in operating conditions (temperature, pressure ...) independent or not, of preferably independent of the operating conditions of the distillation zone.
  • operating conditions are generally as follows. Absolute pressure required is generally between 0.1 and 6 MPa.
  • Operating temperature is generally between 30 and 400 ° C.
  • the spatial speed within said reaction zone, calculated with respect to the catalyst, is generally understood between 0.5 and 60 h-1.
  • the hydrogen flow rate corresponding to the stoichiometry of the conversion reactions carried out is 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 1.
  • 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 operating 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 relative 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 ratio of reflux within the meaning of this description denotes the ratio of mass flow of the reflux on the mass flow of supply to 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 find in reduced form at least for 50% by weight of its totality. But all other hydrogenation catalyst known to those skilled in the art can also be selected.
  • 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.
  • FIGS. 1 and 2 are each an illustration of a possibility of carrying out the method according to the invention. Similar devices are shown by the same figures in all the figures.
  • a first embodiment of the process is shown in Figure 1.
  • the charge of hydrocarbons is sent to column 2 via line 1.
  • Said column contains distillation internals, which are for example in the case shown in FIG. 1 of the plates or of the lining, represented in part by lines dotted on said figure.
  • the least volatile fraction of the reformate is recovered by the line 5, part is reboiled in exchanger 6 and part is evacuated by line 7.
  • the reboiling steam is reintroduced into the column by line 8.
  • the stabilized liquid distillate is extracted via line 18, the hydrogen and the light hydrocarbons are sent by line 9 to a condenser 10 then in a flask 11 from which they are extracted by line 14 in the form of a purge steam.
  • the liquid phase of the balloon 11 is partially returned via line 12, in column head to ensure reflux, and another part of the liquid phase can be picked up by line 13.
  • the process is the same as that described in figure 1 with the difference that one extracts the liquid distillate through line 18 at a level in the column below the level of reintroduction of the hydrocarbon feedstock into the column by the line 17.
  • This example implements the method as described in the patent application of the applicant EP 0.781.830 A1, and refers to FIG. 1 of the said patent application to which a third reactor 3c is added.
  • a metal distillation column with a diameter of 2.90 m is used, the column comprises from the head to the foot 45 theoretical plates which are numbered from top to bottom (including condenser and reboiler). The power of reboiling is then 8900 kw.
  • Three hydrogenation reactors are used located outside the distillation column which together contain 37.4 m 3 of catalyst.
  • the charge for the column is injected through line 1 into plate 33.
  • the charges for the three reactors 3a, 3b and 3c are withdrawn from plates 6, 8 and 10 respectively via lines 15a, 15b and 15c.
  • the hydrogen is introduced via lines 4a, 4b and 4c before entering the reactors operating in downflow and at 1.5 MPa absolute pressure.
  • the reactors are charged respectively with 4.4, 13.4 and 16.6 m 3 of nickel catalyst sold by the company PROCATALYSE under the reference LD746.
  • the reactor positioned at the bottom of the column contains the least amount of catalyst.
  • the hydrogen / benzene molar ratio is 3.1.
  • the absolute pressure of the reflux tank is 0.5 MPa, the reflux temperature is 50 ° C.
  • the temperature of the liquid before mixing with hydrogen is between 120 and 150 ° C and that of hydrogen is 25 ° C.
  • Weight ratio reflux / charge is 1.72.
  • Example 2 The unit of Example 2 is shown in Figure 2 appended to the text of the this request.
  • a distillation column having a diameter of 1.83 m is used.
  • the same catalyst is used, the same feed as in Example 1, but it is operated here with a single hydrogenation reactor located outside the distillation column.
  • the charge for the column is injected through line 1 into plate 33.
  • the charge for reactor 3 is drawn off from plate 12 via line 15.
  • Hydrogen is introduced through line 4 before entering the reactor operating in flow down and under 1.5 MPa.
  • the reactor is loaded with 8 m 3 of LD746 catalyst.
  • the hydrogen / benzene molar ratio is 3.1.
  • the effluent from reactor 3 is refrodi then re-injected into the column via line 17 to tray 8.
  • the liquid distillate (18) is extracted from tray number 5, hydrogen and light hydrocarbons are extracted from the reflux flask of the column (11) in the form of a steam distillate (14).
  • the absolute pressure at the reflux flask is 0.5 MPa.
  • the simulated compositions of the light reformate (18), purge vapor (14) and heavy reformate (7) fractions are shown in Table 2.
  • Table 3 summarizes the values of the vapor pressure RVP, the amount of benzene present in the final effluent consisting of the stabilized liquid distillate and the column bottom effluent, the reboiling power, the total volume of catalyst used and the diameter of the column in the process according to Example 1 and in the method according to example 2.
  • the traffic in the upper part of the column makes it possible to obtain a light reformate at a vapor pressure RVP (Reid Vapor Pressure) of less than 0.1 MPa.
  • RVP Reid Vapor Pressure
  • the reboiling power is 2.7 times lower in the process according to the present invention compared to the process according to the prior art as described in Example 1.
  • the reflux rate is in the process according to the present invention of 0.6 whereas it is 1.7 in example 1.
  • Another advantage of the process according to the present invention is that for superior performance, only 8 m 3 of catalyst is used against 37.4 m 3 in l Example 1.
  • the method according to the present invention makes it possible to reduce the diameter of the column.
  • Examples 4, 5 and 6 describe a process with a column feed different from the charge used in Examples 1 and 2, the charge containing three times more heavy reformate.
  • This example describes a process without stabilization of the distillate with a single reactor hydrogenation located outside of the distillation column and with reintroduction of the hydrogenated charge 4 trays above the level of racking.
  • the column includes 45 theoretical plates (including condenser and reboiler) and with a diameter of 3.50 m.
  • the desired olefin-depleted effluent is withdrawn at the head of the column with the light gases.
  • the level of reintroduction into the column is 4 trays higher than the level of sampling.
  • the unit is similar to that of FIG. 1 appended to the text of the present application but without drawing off at 18.
  • the charge for the column is injected by line 1 into the tray 33.
  • the charge for the reactor 3 is drawn off from the board 12 via line 15.
  • Hydrogen is introduced via line 4 before entering the reactor operating in downflow and at 1.5 MPa absolute pressure.
  • the reactor is loaded with 12 m 3 of LD746 catalyst.
  • the hydrogen / benzene molar ratio is 2.8.
  • the effluent from reactor 3 is cooled by an exchanger and is then re-injected into the column via line 17 on the plate 8.
  • the absolute pressure in the reflux tank is 0.5 MPa.
  • the simulated compositions of the light reformate (13), purge vapor (14) and heavy reformate (7) fractions are shown in Table 4. The performances are shown in Table 7.
  • the reflux rate is 0.40.
  • the reboiling power is 15,660 kw.
  • the process has a configuration in accordance with the invention with withdrawal of a stabilized liquid distillate below the drawing off of a steam distillate and with a level of reintroduction of the hydrogenated charge 4 trays above the racking tray.
  • the unit is shown in Figure 2.
  • the column includes 45 theoretical plates (including condenser and reboiler) and has a diameter of 3.20 m.
  • the reflux rate compared to food is 0.51.
  • the power of reboiling is 13,370 kw.
  • the process is carried out with an external hydrogenation reactor containing 12 m 3 of catalyst and operating at an absolute pressure of 1.5 MPa.
  • the same catalyst is used, the same charge as those described in Example 4, but the procedure is according to the present invention, that is to say that the stabilized liquid distillate (light reformate) is recovered from the plate 5 and the steam distillate at the top of the column.
  • the charge for the column is injected through line 1 into plate 33.
  • the charge for reactor 3 is drawn off from plate 12 via line 15.
  • Hydrogen is introduced through line 4 before entering the reactor operating in flow falling and under 1.5 MPa of absolute pressure.
  • the reactor is loaded with 12 m 3 of LD746 catalyst.
  • the hydrogen / benzene molar ratio is 3.0.
  • the effluent from reactor 3 is cooled and then re-injected into the column via line 17 on plate 8.
  • the absolute pressure in the reflux flask is 0.5 MPa.
  • Example 4 it achieves conversion performance greater than those described in Example 4, 0.46% by volume of benzene is obtained in the product formed by the mixture of light reformate and heavy reformate instead of 0.59% vol. in example 4 while in example 4 we increased by around 20% reboiling power compared to that used in this example.
  • the column includes 45 theoretical plates (including condenser and reboiler) and has a diameter of 3.05 m.
  • the charge for the column is injected through line 1 into tray 33.
  • the charge for reactor 3 is withdrawn from tray 12 via line 15.
  • Hydrogen is introduced through line 4 before entering the reactor operating in downward flow and under 1.5 MPa absolute pressure.
  • the reactor is loaded with 20.4 m 3 of LD746 catalyst.
  • the hydrogen / benzene molar ratio is 2.9.
  • the effluent from reactor 3 is cooled and then re-injected into the column via line 17 to tray 5.
  • the liquid distillate (18) is withdrawn from tray 6 under the return of line 17.
  • the absolute pressure in the reflux tank is 0.5 MPa.
  • the simulated compositions of the light reformate (13), purge vapor (14) and heavy reformate (column bottom effluent) (7) fractions are shown in Table 6.
  • the performances are shown in Table 7.
  • the method according to this implementation makes it possible to work with a low reboiling power for a conversion to benzene as good as that known methods.
  • Table 7 summarizes the values of the vapor pressure RVP, the amount of benzene present in the final effluent consisting of the stabilized liquid distillate and the column bottom effluent, the reboiling power and the total volume of catalyst used.
  • the method according to the invention makes it possible to operate with a device for distillation of lower circumference.
  • one of the implementations of the method according to the present invention in which the reactor is completely external makes it possible to have a lower reboiling power, that is to say that there is an energy saving spent in the exchanger 6 for vaporizing part of the least volatile fraction of the reformate recovered at the bottom of the column and reintroduced into the column.
  • Composition and flow rate of the feed and effluents for example 1.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP99400738A 1998-04-06 1999-03-25 Verfahren zur Umsetzung von Kohlenwasserstoffen durch Behandlung in einer mit einer Reaktionszone verbundenen Distillationsanlage und Anwendung fur die Hydrogeniering von Benzol Expired - Lifetime EP0949315B1 (de)

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FR9804351A FR2777012B1 (fr) 1998-04-06 1998-04-06 Procede de conversion d'hydrocarbures par traitement dans une zone de distillation comprenant le soutirage d'un distillat stabilise, associee a une zone reactionnelle, et son utilisation en hydrogenation du benzene
FR9804351 1998-04-06

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EP0949315A1 true EP0949315A1 (de) 1999-10-13
EP0949315B1 EP0949315B1 (de) 2005-08-03

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DE (1) DE69926430T2 (de)
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US6855853B2 (en) * 2002-09-18 2005-02-15 Catalytic Distillation Technologies Process for the production of low benzene gasoline
FR2933987B1 (fr) * 2008-07-18 2010-08-27 Inst Francais Du Petrole Procede d'hydrogenation du benzene
CN101649221B (zh) * 2008-08-13 2012-12-12 中国石油天然气股份有限公司 一种汽油轻馏分和中馏分生产重整原料的方法
US7910070B2 (en) * 2008-12-09 2011-03-22 Uop Llc Process for reducing benzene concentration in reformate
FR2948380B1 (fr) * 2009-07-21 2011-08-12 Inst Francais Du Petrole Procede de reduction selective de la teneur en benzene et en composes insatures legers de differentes coupes hydrocarbures
EP2277980B1 (de) * 2009-07-21 2018-08-08 IFP Energies nouvelles Verfahren zur selektiven reduzierung des benzolgehalts und des gehalts an leichten ungesättigten verbindungen von verschiedenen kohlenwasserstoffverschnitten
CN103998578B (zh) 2012-02-01 2016-08-17 沙特阿拉伯石油公司 用于生产降苯汽油的催化重整方法和系统

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EP0781830A1 (de) * 1995-12-27 1997-07-02 Institut Francais Du Petrole Verfahren zur Erniedrigung des Gehaltes von Benzol und von leichten ungesättigten Verbindungen in Kohlenwasserstofffraktionen

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US3926785A (en) * 1971-11-01 1975-12-16 Chevron Res Integrated distillation and hydrodesulfurization process for jet fuel production
EP0781830A1 (de) * 1995-12-27 1997-07-02 Institut Francais Du Petrole Verfahren zur Erniedrigung des Gehaltes von Benzol und von leichten ungesättigten Verbindungen in Kohlenwasserstofffraktionen

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DE69926430D1 (de) 2005-09-08
JP4348657B2 (ja) 2009-10-21
ES2246560T3 (es) 2006-02-16
CA2265991C (fr) 2009-06-23
FR2777012A1 (fr) 1999-10-08
US6261442B1 (en) 2001-07-17
EP0949315B1 (de) 2005-08-03
DE69926430T2 (de) 2006-01-26
FR2777012B1 (fr) 2000-08-25
CA2265991A1 (fr) 1999-10-06
JPH11323357A (ja) 1999-11-26

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