EP0781831B1 - Verfahren zur Erniedrigung des Gehaltes von Benzol und von leichten ungesättigten Verbindungen in Kohlenwasserstofffraktionen - Google Patents

Verfahren zur Erniedrigung des Gehaltes von Benzol und von leichten ungesättigten Verbindungen in Kohlenwasserstofffraktionen Download PDF

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EP0781831B1
EP0781831B1 EP96402910A EP96402910A EP0781831B1 EP 0781831 B1 EP0781831 B1 EP 0781831B1 EP 96402910 A EP96402910 A EP 96402910A EP 96402910 A EP96402910 A EP 96402910A EP 0781831 B1 EP0781831 B1 EP 0781831B1
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Prior art keywords
zone
hydrogenation
process according
hydrogen
distillation
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French (fr)
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EP0781831A1 (de
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Christine Travers
Jean Cosyns
Charles Cameron
Jean-Luc Nocca
Francoise Montecot
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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
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/04—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps
    • C10G65/08—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only refining steps at least one step being a hydrogenation of the aromatic hydrocarbons
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/02—Gasoline

Definitions

  • the invention relates to a process for the selective reduction of the content of light unsaturated compounds (that is to say containing at most six carbon atoms per molecule) including benzene, of a hydrocarbon fraction essentially comprising at least 5 carbon atoms per molecule, without appreciable loss of the octane number, said process comprising passing said cut through a distillation zone associated with a hydrogenation reaction zone, followed by the passage of part of the effluent of the distillation zone mainly comprising C 5 -C 6 hydrocarbons, that is to say containing 5 and / or 6 carbon atoms per molecule, in a zone for isomerization of paraffins.
  • 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.
  • fuels reformulated must not contain more than 1% benzene; in Europe, even if the specifications are not yet as strict, it is recommended to tighten gradually 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.
  • a first way consists in limiting, in the naphtha constituting the charge of a catalytic reforming unit, the content of benzene precursors, such as cyclohexane and methylcyclopentane. This solution effectively allows significantly reduce the benzene content of the effluent from the reforming unit but cannot be sufficient on its own when it comes to descending to levels as well low than 1%.
  • a second way consists in eliminating, by distillation, a fraction slight reformate containing benzene. This solution leads to a loss of around 15 to 20% of hydrocarbons which could be used in gasoline.
  • a third way is to extract the benzene present in the effluent from the unit reforming.
  • Benzene from a reformate can also be hydrogenated to cyclohexane. Since it is impossible to selectively hydrogenate benzene from a mixture hydrocarbons also containing toluene and xylenes, so it's necessary to fractionate this mixture beforehand so as to isolate a cut containing only benzene, which can then be hydrogenated. It also been described a process in which the benzene hydrogenation catalyst is included in the rectification zone of the distillation column which separates the benzene from other aromatics (Benzene Reduction - Kerry Rock and Gary Gildert CDTECH - 1994 Conference on Clean Air Act Implementation and Reformulated Gasoline - Oct. 94), which saves money of equipment.
  • the hydrogenation of benzene from a reformate leads to a loss of octane number.
  • This loss of octane can be compensated by the addition of compounds of index high octane, for example ethers such as MTBE or ETBE, or branched paraffinic hydrocarbons.
  • ethers such as MTBE or ETBE
  • branched paraffinic hydrocarbons can be generated from the reformate itself, by isomerization of linear paraffins.
  • the isomerization catalysts for linear paraffins and branched paraffins are not inactive vis-à-vis hydrocarbons from other chemical families.
  • the method according to the invention avoids the disadvantages mentioned, that is to say it allows to produce at a lower cost, from a raw reformate, a reformate depleted in benzene or, if necessary, almost completely stripped of benzene and others unsaturated hydrocarbons containing not more than six carbon atoms per molecule such as light olefins, without significant loss of yield, and with very little loss or gain in octane rating.
  • the process is characterized by the integration of the three distillation operations, of hydrogenation and isomerization arranged and operated so as to avoid less in part, preferably in most part, training, by azeotropy with benzene, cyclohexane and isoparaffins with 7 carbon atoms by molecule, in the distillate which is directed to isomerization. So the process according to the invention at least partially performs the selective hydrogenation of benzene and of any unsaturated compound comprising not more than six carbon atoms per molecule and different from benzene, possibly present in the feed.
  • the charge which feeds the distillation zone is introduced into said zone generally at least at a level of said area, preferably mainly at one level of said area.
  • 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 generally at least equal to five theoretical stages.
  • the reaction zone is at least partially internal to the distillation
  • the rectification zone or the exhaustion zone, and preferably the exhaustion zone can usually be in at least one column different from the column comprising the internal part of the reaction zone.
  • the hydrogenation reaction zone generally comprises at least one bed hydrogenation catalytic, preferably from 1 to 4 catalytic bed (s); in the case where at least two catalytic beds are incorporated in the zone distillation, these two beds are optionally separated by at least one internal distillation.
  • the hydrogenation reaction zone performs at least partially the hydrogenation of the benzene present in the feed, generally in such a way that the benzene content of the overhead effluent is at the maximum equal to a certain content, and said reaction zone achieves at least in part, preferably for the most part, the hydrogenation of any unsaturated compound comprising at most six carbon atoms per molecule and different from benzene, possibly present in the load.
  • the method according to the invention is such that the hydrogenation reaction zone is at least in part, of preferably entirely, internal to the distillation zone. So, for the part of the reaction zone internal to the distillation zone, the liquid sample is naturally made by flow in the part of the internal reaction zone to the distillation zone, and the reintroduction of the effluent into the distillation zone is done also naturally by flow of the liquid from the reaction zone internal to the distillation zone so as to ensure the continuity of the distillation.
  • the method according to the invention is preferably such that the flow of the liquid to be hydrogenated is co-current to the flow of the gas stream comprising hydrogen, for any catalytic bed in the internal part of the zone hydrogenation, and even more preferably such as the flow of liquid to hydrogenate is co-current to the flow of the gas stream comprising hydrogen and such that the distillation vapor is separated from said liquid, for any bed catalytic of the internal part of the hydrogenation zone.
  • the method according to the invention is such that the area hydrogenation reaction is at least in part, preferably in whole, external to the distillation zone. Then the effluent from at least one catalytic bed of the external part of the hydrogenation zone is generally reintroduced substantially close to a level of sampling, preferably the level of sample which fed said catalytic bed.
  • the process according to the invention comprises from 1 to 4 level (s) of sampling which feed (s) the part external of the hydrogenation zone. So two cases can arise.
  • the external part of the hydrogenation zone is supplied by a single level of withdrawal, and then, if said part comprises at least two beds catalytic distributed in at least two reactors, said reactors are arranged in series or in parallel.
  • the external part of the hydrogenation zone is supplied by at least two levy levels.
  • the method according to the invention is such that the hydrogenation zone is both partially incorporated into the hydrogenation zone distillation, i.e. internal to the distillation zone, and partially external to the distillation zone.
  • the hydrogenation zone comprises at least two catalytic beds, at least one catalytic bed being internal at the distillation zone, and at least one other catalytic bed being external to the zone distillation.
  • each catalytic bed is supplied by a single level of sampling, preferably associated with a single level where the effluent said catalytic bed of the external part of the hydrogenation zone is reintroduced, said level of withdrawal being distinct from the level of withdrawal which supplies the other (s) catalytic bed (s).
  • the liquid to be hydrogenated either partially, or totally, first circulates in the external part of the area hydrogenation then the internal part of said zone.
  • the part of the area reaction internal to the distillation zone has the characteristics described in the first embodiment.
  • the part of the reaction zone external to the zone distillation has the characteristics described in the second embodiment.
  • the method according to the invention is such that the flow of the liquid to be hydrogenated is co-current or counter-current, from preferably co-current, to the flow of the gas stream comprising hydrogen, for any catalytic bed in the hydrogenation zone.
  • the theoretical molar ratio of hydrogen necessary for the desired conversion of benzene is 3.
  • the quantity of hydrogen distributed, in the gas flow, before or in the zone of hydrogenation is optionally in excess with respect to this stoichiometry, and all the more so since it is necessary to hydrogenate, in addition to the benzene present in the feed, at least partially any unsaturated compound comprising at most six carbon atoms per molecule and present in said charge.
  • the excess hydrogen if it exists, 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 top of the distillation zone is recovered, then compressed and reused in the hydrogenation zone.
  • the excess hydrogen which leaves the top of the distillation zone is recovered, then compressed and reused in the isomerization zone.
  • the hydrogen used according to the invention for the hydrogenation of unsaturated compounds containing at most six carbon atoms per molecule, and included in the flux gaseous can come from all sources producing hydrogen at least 50 % purity volume, preferably at least 80% purity volume and so even more preferred at least 90% purity volume.
  • hydrogen from catalytic reforming processes, methanation, P.S.A. (alternating pressure adsorption), electrochemical generation, steam cracking or steam reforming.
  • the hydrogen injected into the hydrogenation process passes first by the isomerization step. In such a case, hydrogen is injected into the unit isomerization to delay deactivation of the isomerization catalyst by carbon deposition. Unconsumed hydrogen from the isomerization zone can then be purified and used in the hydrogenation unit.
  • 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 isomerization effluent.
  • the mixture thus obtained can, after possible stabilization, be used as fuel either directly, or by incorporation into the fuel fractions.
  • the operating conditions are judiciously chosen, in relation to the nature of the load and other parameters known to the specialist in reactive distillation, such as the distillate / charge ratio, in such a way that the overhead effluent from the distillation zone is practically free of cyclohexane and isoparaffins comprising 7 carbon atoms per molecule.
  • the method according to the invention is generally and preferably such that the overhead effluent from the distillation zone is practically free of cyclohexane and isoparaffins comprising 7 carbon atoms per molecule.
  • the hydrogenation catalyst can be placed in said part incorporated according to the different technologies proposed to drive catalytic distillations. They are essentially of two types.
  • reaction and distillation proceed simultaneously in the same physical space, as taught for example patent application WO-A-90 / 02.603, patents US-A-4,471,154, US-A-4.475.005, US-A-4.215.011, US-A-4.307.254, US-A-4.336.407, US-A-4.439.350, US-A-5.189.001, US-A-5.266.546, US-A-5.073.236, US-A-5.215.011, US-A-5.275.790, US-A-5.338.517, US-A-5.308.592, US-A-5,236,663, US-A-5,338,518, as well as patents EP-B1-0,008,860, EP-B1-0,448,884, EP-B1-0,396,650 and EP-B1-0,494,550 and the patent application EP-A1-0.559.511.
  • the catalyst is then generally in contact with a descending liquid phase, generated by the reflux introduced at the top of the zone distillation, and with an ascending vapor phase, generated by the vapor of rewetting introduced at the bottom of the zone.
  • the flow gaseous comprising hydrogen necessary for the reaction zone, for the carrying out the process according to the invention, could be joined to the vapor phase, substantially at the inlet of at least one catalytic bed of the reaction zone.
  • the catalyst is arranged in such a way that reaction and distillation generally proceed independently and consecutive, as taught for example by patents US-A-4,847,430, US-A-5,130,102 and US-A-5,368,691, the steam from the distillation zone does not practically not passing through any catalytic bed in the reaction zone.
  • the process according to the invention is generally such that the flow of the liquid to hydrogenate is co-current to the flow of the gas stream comprising hydrogen and such that the distillation vapor is practically not in contact with the catalyst (which generally translates in practice into the fact that said vapor is separated from said liquid to be hydrogenated), for any catalytic bed of the part internal of the hydrogenation zone.
  • any catalytic bed of the part of the reaction zone which is in the distillation zone is generally such that the gas stream comprising the hydrogen and the flow of the liquid which will react circulate cocurrently, generally ascending, through said bed, even if overall, in the distillation zone catalytic, the gas stream comprising hydrogen and the liquid stream which will react flow against the tide.
  • Such systems generally include less a liquid distribution device which can be for example a liquid distributor, in any catalytic bed in the reaction zone.
  • these technologies were designed for reactions catalytic agents intervening between liquid reagents, they cannot be suitable without modification for a catalytic hydrogenation reaction, for which one of the reactants, hydrogen, is in the gaseous state.
  • the part internal of the hydrogenation zone includes at least one distribution device liquid and at least one gas flow distribution device comprising hydrogen, for any catalytic bed in the internal part of the zone hydrogenation.
  • the flow distribution device gas containing hydrogen is disposed before the dispensing device liquid, and therefore before the catalytic bed.
  • the gas flow distribution device comprising hydrogen is disposed at the level of the liquid distribution device, so that the gas flow comprising hydrogen is introduced into the liquid before the catalytic bed.
  • the gas flow distribution device comprising hydrogen is disposed after the distribution device for liquid, and therefore within the catalytic bed, preferably not far from said device distribution of the liquid in said catalytic bed.
  • the terms "before” and “after” used above are understood with respect to the direction of circulation of the liquid which will cross the catalytic bed, that is to say generally in the ascending direction.
  • One of the preferred embodiments of the method according to the invention is such that the catalyst of the internal part of the hydrogenation zone is arranged in the zone reaction according to the basic device described in patent US-A-5,368,691, arranged so that any internal catalytic bed in the distillation zone is supplied by a gas stream comprising hydrogen, regularly distributed at its base, for example according to one of the three techniques described above.
  • the distillation zone consists of a single column and if the hydrogenation zone is entirely internal to said column, the catalyst included in any catalytic bed, internal to the distillation zone, is then in contact with an ascending liquid phase, generated by the reflux introduced at the top of the distillation column, and with the gas stream comprising hydrogen which flows in the same direction as the liquid; contact with the vapor phase of the distillation is avoided by passing it through at least one chimney specially furnished.
  • 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 zone head temperature is generally between 40 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 a pressure between 2 and 20 bar, preferably between 4 and 10 bar.
  • the liquid subjected to hydrogenation is supplied by 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 catalyst placed in said external part is according to any known technology skilled in the art under operating conditions (temperature, pressure, etc.) independent or not, preferably independent, of the operating conditions from the distillation zone.
  • the pressure required for this hydrogenation stage is generally between 1 and 60 bar absolute, preferably between 2 and 50 bar and even more preferably between 5 and 35 bar.
  • the operating temperature of the external part 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 the external part of said hydrogenation zone, calculated with respect to the catalyst, is generally between 1 and 50 and more particularly between 1 and 30 h -1 (volume of charge per volume of catalyst and per hour ).
  • the hydrogen flow rate corresponding to the stoichiometry of the hydrogenation reactions involved is between 0.5 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 catalyst used in the hydrogenation zone generally comprises at least one metal chosen from the group formed by nickel and platinum, used as it is or preferably deposited on a support.
  • the metal should generally be under reduced form at least for 50% by weight of its whole. But any other hydrogenation catalyst known to those skilled in the art can also be selected.
  • the catalyst can advantageously contain at least one halogen in a proportion by weight relative to the catalyst of between 0.2 and 2%.
  • chlorine or fluorine or a combination of the two is used in a proportion relative to the total weight of catalyst of between 0.2 and 1.5%.
  • a catalyst is generally used such that the average size of the platinum crystallites is less than 60.10 -10 m, preferably less than 20.10 -10 m, even more so preferred less than 10.10 -10 m.
  • the total proportion of platinum relative to the total weight of catalyst is generally between 0.1 and 1% and preferably between 0.1 and 0.6%.
  • 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 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.
  • the isomerization catalyst used in the isomerization zone according to the present invention is generally of two types. But any other catalyst isomerization known to those skilled in the art can also be chosen.
  • the first type of catalyst is based on alumina.
  • it includes minus one metal from group VIII of the periodic table and one support comprising alumina.
  • it further comprises at least one halogen, preferably chlorine.
  • a preferred catalyst according to the present invention comprises at least one group VIII metal deposited on a support consisting of eta alumina and / or gamma alumina, that is to say that for example said support consists of alumina eta and gamma alumina, the alumina eta content being between 85 and 95% by weight relative to the support, preferably between 88 and 92% by weight, and even more preferably between 89 and 91% by weight, the complement to 100% by weight of the support consisting of gamma alumina.
  • the catalyst support can also for example consist essentially gamma alumina.
  • the group VIII metal is preferably chosen from the group formed by platinum, palladium and nickel.
  • the alumina was optionally used in the present invention has a specific surface generally between 400 and 600 m 2 / g and preferably between 420 and 550 m 2 / g, and a total pore volume generally between 0.3 and 0 , 5 cm 3 / g and preferably between 0.35 and 0.45 cm 3 / g.
  • the gamma alumina optionally used in the present invention generally has a specific surface of between 150 and 300 m 2 / g and preferably between 180 and 250 m 2 / g, a total pore volume generally between 0.4 and 0.8 cm 3 / g and preferably between 0.45 and 0.7 cm 3 / g.
  • alumina when used as a mixture, are mixed and shaped, in proportions defined by any known technique of a person skilled in the art, for example by extrusion through a die, by pastillage or coating.
  • a second type of catalyst used in the isomerization zone according to the process of the present invention is a zeolite-based catalyst, that is to say comprising at least one group VIII metal and a zeolite.
  • zeolite-based catalyst that is to say comprising at least one group VIII metal and a zeolite.
  • Different zeolites can be used for said catalyst; said zeolite is preferably chosen from the group formed by mordenite or omega ⁇ zeolite.
  • Use is preferably made of a mordenite having an Si / Al (atomic) ratio of between 5 and 50 and preferably between 5 and 30, a sodium content of less than 0.2% and preferably of less than 0.1% ( relative to the weight of dry zeolite), a volume of mesh V of the elementary mesh of between 2.78 and 2.73 nm 3 and preferably between 2.77 and 2.74 nm 3 , an absorption capacity of benzene greater than 5% and preferably greater than 8% (relative to the weight of dry solid).
  • the mordenite thus prepared is then mixed with a generally amorphous matrix (alumina, silica alumina, kaolin, ...) and shaped by any method known to those skilled in the art (extrusion, pelletizing, coating).
  • the mordenite content of the support thus obtained must be greater than 40% and preferably greater than 60% by weight.
  • a catalyst based on an omega ⁇ or mazzite zeolite has a SiO 2 / Al 2 O 3 molar ratio of between 6.5 and 80, preferably between 10 and 40, a sodium content by weight of less than 0.2%, preferably of less than 0.1%, per relative to the weight of dry zeolite.
  • Its porous distribution generally comprises between 5 and 50% of the pore volume contained in pores with radius (measured by the BJH method) located between 1.5 and 14 nm, preferably between 2.0 and 8.0 nm (mesopores).
  • its DX crystallinity level is greater than 60%.
  • the zeolitic support thus obtained has a specific surface generally between 300 and 550 m 2 / g and preferably between 350 and 500 m 2 / g and a pore volume generally between 0.3 and 0.6 cm 3 / g and of preferably between 0.35 and 0.5 cm 3 / g.
  • At least one hydrogenating metal from group VIII preferably chosen from the group formed by platinum, palladium and nickel, is then deposited on this support, by any technique known to a person skilled in the art, for example in the case of platinum by anion exchange in the form of hexachloroplatinic acid when the support is alumina and by cation exchange with platinum chloride tetramine when the support is a zeolite.
  • the content by weight is between 0.05 and 1% and preferably between 0.1 and 0.6%.
  • the content by weight is between 0.1 and 10% and preferably between 0.2 and 5%.
  • the isomerization catalyst thus prepared can be reduced under hydrogen.
  • said catalyst is subjected to a halogenation treatment, preferably chlorination, with any compound halogenated, preferably chlorinated, known to those skilled in the art such as for example carbon tetrachloride or perchlorethylene.
  • the halogen content, preferably in chlorine, the final catalyst is preferably between 5 and 15% by weight and preferably between 6 and 12% by weight.
  • This treatment halogenation, preferably chlorination, of the catalyst can be carried out either directly in the unit before injection of the charge ("in-situ") or off site. In in such a case, it is also possible to carry out the halogenation treatment, chlorination preference, prior to catalyst reduction treatment under hydrogen.
  • the operating conditions used in the isomerization zone are generally those described below, depending on the type of catalyst.
  • the temperature is generally between 80 and 300 ° C and preferably between 100 and 200 ° C.
  • the partial pressure of hydrogen is between 0.1 and 70 bar and preferably between 1 and 50 bar.
  • the space velocity is between 0.2 and 10, preferably between 0.5 and 5 liters of liquid hydrocarbons per liter of catalyst per hour.
  • the molar ratio of hydrogen to hydrocarbons at the entrance to the zone isomerization is such that the molar ratio of hydrogen to hydrocarbons in the isomerate is greater than 0.06 and preferably between 0.06 and 10.
  • the temperature is generally between 200 and 300 ° C and preferably between 230 and 280 ° C
  • the partial pressure of hydrogen is between 0.1 and 70 bar and preferably between 1 and 50 bar.
  • the space velocity is generally between 0.5 and 10, preferably between 1 and 5 liters of liquid hydrocarbons per liter of catalyst per hour.
  • the report molar hydrogen on hydrocarbons in the isomerate can vary between wide limits and is generally between 0.07 and 15 and preferably between 1 and 5.
  • FIGS. 1 to 3 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.
  • FIG. 1 A first embodiment of the process is shown in FIG. 1.
  • the crude C 5 + reformate generally containing small quantities of C 4 - hydrocarbons, is sent to a column 2 by line 1.
  • Said column contains distillation internals, which are for example in the case shown in Figure 1 of the plates or the lining, represented in part by dotted lines in said figure. It also contains at least one internal catalytic 3 containing a hydrogenation catalyst, which can be alternated with the internal distillation.
  • the catalytic internals are supplied at their base, by lines 4c and 4d, by hydrogen coming from lines 4, then 4a and 4b.
  • the least volatile fraction of the reformate consisting mainly of hydrocarbons with 7 carbon atoms and more, is recovered by line 5, reboiled in exchanger 6 and evacuated by line 7. Steam reboiling is reintroduced into the column by line 8.
  • the vapor of light hydrocarbons that is to say comprising mainly 6 carbon atoms and less per molecule, is sent by line 9 into a condenser 10 then in a flask 11 where there is a separation between a liquid phase and a vapor phase mainly consisting of excess hydrogen possibly sent by lines 16 then 4a then 4b then 4c or 4d.
  • the vapor phase is evacuated from the balloon by lines 14 then 15. A fraction is possibly recycled to the column by line 16, after being put back in pressure by means of a device not shown in FIG. 1.
  • the liquid phase of the flask 11 is partly returned, by line 12, to the top of column to ensure reflux.
  • the other part is directed by lines 13 then 17 to the isomerization reactor 18.
  • a stream of hydrogen is there possibly added by lines 4 then 4a.
  • the isomerate is recovered by the line 19, cooled, and sent to a flask 20 where a vapor phase separates consisting essentially of hydrogen, which is evacuated by lines 22 then 23, and possibly recycled after purification to the hydrogen circuit by the line 24 then by lines 4a, 4b, and 4c or 4d.
  • the liquid phase is drawn off via line 21 and constitutes, after stabilization if necessary, a component for essences, almost free of compounds unsaturated comprising at most 6 carbon atoms per molecule, of octane number Student.
  • the crude C 5 + reformate is sent by line 1 to a distillation column 2, provided with distillation internals which are, for example in the case of FIG. 2, distillation plates, as well as a withdrawal (or sampling) plate of liquid phase.
  • the liquid phase withdrawn from the withdrawal plate by line 25 is brought into contact with hydrogen supplied by lines 4, 4a and 4b, and directed to a hydrogenation reactor 33.
  • the hydrogenation reactor can operate either by upward flow, ie downward flow as shown in FIG. 2.
  • the effluent from this reactor is recovered by line 26 and recycled to the distillation column by lines 27 then 32, generally in the upper part of the distillation zone located under the racking plate near said plate. It is generally considered that a maximum of four hydrogenation reactors can constitute the hydrogenation zone, in the case where it is external to the distillation zone, regardless of the number of sampling level (s).
  • all or part of the reactor effluent recovered by line 26 is cooled (exchanger not shown) and directed by line 28 to the balloon 29 where a vapor phase rich in hydrogen separates, evacuated by the line 30, and a liquid phase which is recycled to column 2 by lines 31 and 32.
  • the head and bottom column effluents are treated as described above. for the first realization of the process.
  • the area of hydrogenation is shared between an internal part of the distillation column, as described for the first version of the process, and a part external to this column, as described for the second version of the process.
  • a metal distillation column with a diameter of 50 mm is used, made adiabatic by heating envelopes whose temperatures are regulated so as to reproduce the temperature gradient which is established in the column.
  • the column includes, from head to toe: a zone of rectification composed of 11 perforated trays with weir and descent, one hydrogenating catalytic distillation zone and a compound exhaustion zone of 63 perforated trays.
  • the hydrogenating catalytic distillation zone is consisting of three catalytic distillation doublets, each doublet being formed by a catalytic cell surmounted by three plates perforated. The detail of construction of a catalytic cell as well as its arrangement in the column are shown schematically for information in Figure 4.
  • the catalytic cell 41 consists of a cylindrical container with a flat bottom, of a outer diameter 2 mm lower than the lower diameter of the column. She is provided at its lower part, above the bottom, with a grid 42 which serves both support for the catalyst and liquid distributor for hydrogen, and its upper part, of a catalyst retaining grid 43, the height of which can be varied.
  • the catalyst 44 fills the entire volume between these two grids.
  • the catalytic cell receives the liquid from the upper distillation stage 45, by the descent 46. After having traversed the cell in the ascending direction, the liquid is discharged by overflow through the descent 47 and flows onto the tray lower distillation 48.
  • the vapor from the lower plate 48 borrows the central chimney 49 integral with the cell, entering through orifices 50 (a only visible in the figure) and emerging under the upper plate 45 by orifices 51 (only one visible in the figure).
  • Hydrogen is introduced at the foot of the catalytic cell via the tubing 52, then through the orifices 53 (six in total) distributed on the periphery of the cell, in the immediate vicinity of the bottom. Seals sealing 54 prevent any hydrogen leakage before arriving on the bed catalytic.
  • Each of the three cells is packed with 36 g of nickel catalyst sold by the PROCATALYSE under the reference LD 746.
  • 250 g / h of a reformate are introduced essentially hydrocarbons having at least 5 carbon atoms in their molecule, the composition of which is presented in the second column of the table 1.
  • a flow rate of 4.5 Nl / h is also introduced at the base of each cell. hydrogen.
  • the column is brought into operation by establishing an equal reflux rate at 5 and regulating the bottom temperature at 195 ° C and the absolute pressure at 6 bar.
  • the distillate is sent together with hydrogen, with a molar ratio hydrogen / hydrocarbons set at 0.125, in an isomerization reactor containing 57 g of platinum-based catalyst on chlorinated alumina, sold by the company PROCATALYSE under the reference IS612A, operating at a temperature of 150 ° C and a pressure of 30 bar.
  • the isomerization reactor or isomerate effluent has the composition presented in the last column of Table 1.
  • the last three lines of table 1 show the octane numbers RON (Research), MON (Engine) and (RON + MON) / 2 (Medium octane) of the reformate, column effluents and isomerate .
  • the isomerate has an octane index of 3 points higher than the distillate, and can be valued as a fuel component, provided that it is stabilized, that is to say, the rid by distillation of the 3% of constituents very volatiles (C 3 - ) formed during isomerization, mainly by decomposition of isoparaffins with 7 carbon atoms per molecule.
  • compositions (% by weight) and octane numbers of the different streams for example 1 Reformate Residue Distillate Isomerate Hydrocarbons C6 - 26.4 0.20 94.9 97.9 of which: C3- - - - 3.0 olefins 0.19 - - - benzene 4.70 - 0.48 - cyclohexane 0.08 0.19 16.3 6.85 Hydrocarbons C7 + 73.6 99.8 5.1 2.1 of which: isoC7 9.47 11.1 5.1 2.1 toluene 19.7 27.2 - - xylene 20.1 27.7 - - Total 100 100 100 100 100 100 RON 95.5 100.1 77.6 80.5 MY 85.8 89.1 74.5 77.8 (RON + MON) / 2 90.6 94.6 76.1 79.1
  • Example 1 The process described in Example 1 is reproduced, with the same apparatus, the same hydrogenation and isomerization catalysts, and the same conditions operating, except for the distillation column, whose set point for regulating the bottom temperature is fixed at 188 ° C. So the head effluent of the distillation zone is practically free of cyclohexane and of isoparaffins with 7 carbon atoms per molecule.
  • a residue and a distillate are collected at the bottom and at the top of the distillation column, respectively with a flow rate of 195.7 and 54.2 g / h, the compositions and the octane numbers are presented in the third and fourth columns of the table 2.
  • the last column of the table shows the composition and octane numbers of the isomerate.
  • the distillate Compared to Example 1, the distillate has a much lower cyclohexane content and a very low content of isoparaffins with 7 carbon atoms per molecule. Its isomerization allows the average octane number to be raised by more than 10 points, practically without loss in the form of very volatile products (C 3 - ).
  • a reconstituted gasoline is obtained which is almost free of benzene and olefins, having an average octane number equal to 90.8, ie substantially higher than that of the starting reformate, and without significant loss of yield.
  • compositions (% by weight) and octane numbers of the different streams for example 2 Reformate Residue Distillate Isomerate Hydrocarbons C6 - 26.4 6.1 99.9 99.9 of which: C3- - - - 0.08 olefins 0.19 - - - benzene 4.70 0.01 0.54 - cyclohexane 0.08 5.83 0.43 1.27 Hydrocarbons C7 + 73.6 93.9 0.18 0.1 of which: isoC7 9.47 12.1 0.18 0.1 toluene 19.7 25.2 - - xylene 20.1 25.6 - - Total 100 100 100 100 100 100 RON 95.5 98.5 72.5 83.3 MY 85.8 87.6 71.6 82.3 (RON + MON) / 2 90.6 93.1 72.1 82.8

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Claims (31)

  1. Verfahren zur Behandlung einer zum überwiegenden Teil aus Kohlenwasserstoffen mit wenigstens 5 Kohlenstoffatomen pro Molekül bestehenden Charge und wenigstens einer ungesättigten Verbindung mit höchstens 6 Kohlenstoffatomen pro Molekül, darunter Benzol, umfassend, wobei man:
    diese Charge in einer Destillationszone, welche eine Rückhaltezone und eine Rektivikationszone umfasst, behandelt, zugeordnet zu einer Hydrierreaktionszone, welche wenigstens über ein katalytisches Bett verfügt, in welchem man die Hydrierung wenigstens eines Teils der ungesättigten Verbindungen realisiert, welche höchstens 6 Kohlenstoffatome pro Molekül umfassen und in der Charge enthalten sind, und zwar in Anwesenheit eines Hydrierkatalysators und eines gasförmigen Wasserstoff umfassenden Stroms, wobei die Charge der Reaktionszone in Höhe eines Entnahmeniveaus entnommen wird und wenigstens einen Teil der in der Rektivikationszone strömenden Flüssigkeit repräsentiert und wobei der Abstrom aus der Reaktionszone wenigstens zum Teil in die Destillationszone derart wieder eingeführt wird, dass die Kontinuität der Destillation sichergestellt wird und derart, dass schließlich am Kopf der Destillationszone ein an ungesättigten Verbindungen mit höchstens 6 Kohlenstoffatomen pro Molekül verarmter Abstrom und am Boden der Destillationszone ein an ungesättigten Verbindungen mit höchstens 6 Kohlenstoffatomen pro Molekül verarmter Abstrom abgezogen wird und
    man wenigstens einen Teil des Abstroms, abgezogen am Kopf der Destillationszone, in einer Isomerierungszone behandelt, wobei dieser Teil Paraffine, die 5 und/oder 6 Kohlenstoffatome pro Molekül enthalten, und zwar in Anwesenheit eines Isomerierungskatalysators, umfasst, derart, dass ein Isomerat erhalten wird.
  2. Verfahren nach Anspruch 1, derart, dass die Destillation unter einem Druck zwischen 2 und 20 bar bei einem Rückflussverhältnis zwischen 1 und 10 realisiert wird, wobei die Temperatur am Kopf der Destillationszone zwischen 40 und 180°C und die Temperatur am Boden der Destillationszone zwischen 120 und 280°C liegt.
  3. Verfahren nach Anspruch 1 oder 2, bei dem die Hydrierreaktionszone sich wenigstens zum Teil innerhalb der Destillationszone befindet.
  4. Verfahren nach einem der Ansprüche 1 oder 2, bei dem sich die Hydrierreaktionszone wenigstens zum Teil außerhalb der Destillationszone befindet.
  5. Verfahren nach Anspruch 1 oder 2, bei dem die Hydrierzone gleichzeitig teilweise in die Rektivikationszone der Destillationszone eingebaut ist und sich teilweise außerhalb der Destillationszone befindet.
  6. Verfahren nach einem der Ansprüche 3 oder 5, derart, dass für den Teil der Hydrierreaktion innerhalb der Destillationszone die Hydrierreaktion bei einer Temperatur zwischen 100 und 200°C und einem Druck zwischen 2 und 20 bar durchgeführt wird und der Durchsatz des die Hydrierzone speisenden Wasserstoffs zwischen dem einfachen und 10-fachen der Menge oder des Durchsatzes entsprechend der Stoechiometrie der auftretenden Hydrierreaktionen liegt.
  7. Verfahren nach einem der Ansprüche 4 oder 5, derart, dass für den Teil der Hydrierreaktion außerhalb der Destillationszone der für diesen Hydrierschritt notwendige Druck zwischen 1 und 60 bar, die Temperatur zwischen 100 und 400°C und die Raumgeschwindigkeit mitten in der Hydrierzone, berechnet auf den Katalysator, im allgemeinen zwischen 1 und 50 h-1 (Volumencharge pro Volumenkatalysator und Stunde) liegt, und die Wasserstoffmenge entsprechend der Stoechiometrie der ablaufenden Hydrierreaktionen zwischen 0,5 und dem 10-fachen dieser Stoechiometrie liegt.
  8. Verfahren nach einem der Ansprüche 3, 5 oder 6, derart, dass der Hydrierkatalysator in Kontakt mit einer flüssigen absteigenden Phase und mit einer aufsteigenden Dampfphase für jedes katalytische Bett des inneren Teils der Hydrierzone steht.
  9. Verfahren nach Anspruch 8, derart, dass der gasförmige Strom, welcher den für die Hydrierzone notwendigen Wasserstoff umfasst, gebunden ist an die Dampfphase im wesentlichen am Eintritt wenigstens eines katalytischen Bettes der Hydrierzone.
  10. Verfahren nach einem der Ansprüche 1 bis 7, derart, dass die Strömung der zu hydrierenden Flüssigkeit im Gleichstrom zur Strömung des gasförmigen Wasserstoff umfassenden Stroms für jedes katalytische Bett des inneren Teils der Hydrierzone sich befindet.
  11. Verfahren nach einem der Ansprüche 3, 5 oder 6, derart, dass die Strömung der zu hydrierenden Flüssigkeit im Gleichstrom zur Strömung des gasförmigen Wasserstoff umfassenden Stroms erfolgt, und dass der Destillationsdampf praktisch nicht in Kontakt mit dem Katalysator für jedes katalytische Bett des inneren Teils der Hydrierzone steht.
  12. Verfahren nach Anspruch 11, derart, dass die Hydrierzone wenigstens eine Verteilervorrichtung für die Flüssigkeit in jedem katalytischen Bett der Zone und wenigstens eine Verteilervorrichtung für den gasförmigen Wasserstoff enthaltenden Strom für jedes katalytische Bett der Hydrierzone innerhalb dieser Zone umfasst.
  13. Verfahren nach Anspruch 12, derart, dass die Verteilervorrichtung für den gasförmigen Wasserstoff enthaltenden Strom vor der Flüssigkeitsverteilervorrichtung angeordnet ist.
  14. Verfahren nach Anspruch 12, derart, dass die Verteilervorrichtung für den gasförmigen Wasserstoff enthaltenden Strom in Höhe der Flüssigkeitsverteilervorrichtung angeordnet ist.
  15. Verfahren nach Anspruch 12, derart, dass die Verteilervorrichtung für den gasförmigen Wasserstoff enthaltenden Strom hinter der Flüssigkeitsverteilervorrichtung angeordnet ist.
  16. Verfahren nach einem der Ansprüche 1 bis 15, derart, dass der Bodenabstrom der Destillationszone wenigstens zum Teil mit dem Isomerierungsabstrom vermischt wird.
  17. Verfahren nach einem der Ansprüche 1 bis 16, derart, dass der Kopfabstrom aus der Destillationszone praktisch frei von Zyklohexan und Isoparaffinen mit 7 Kohlenstoffatomen pro Molekül ist.
  18. Verfahren nach einem der Ansprüche 1 bis 17, derart, dass der in der Hydrierzone verwendete Katalysator wenigstens ein aus der durch Nickel und Platin gebildeten Gruppe gewähltes Metall umfasst.
  19. Verfahren nach einem der Ansprüche 1 bis 18, derart, dass der in der Hydrierzone verwendete Katalysator einen Träger umfasst.
  20. Verfahren nach einem der Ansprüche 1 bis 19, derart, dass der Isomerierungskatalysator wenigstens ein Metall der Gruppe VIII des Periodensystems der Elemente und einen Aluminiumoxid umfassenden Träger aufweist.
  21. Verfahren nach Anspruch 20, derart, dass der Katalysator im übrigen ein Halogen umfasst.
  22. Verfahren nach einem der Ansprüche 20 oder 21, derart, dass die Temperatur zwischen 80 und 300°C, der Wasserstoffpartialdruck zwischen 0,1 und 70 bar, die Raumgeschwindigkeit zwischen 0,2 und 10 Liter flüssiger Kohlenwasserstoffe pro Liter und Katalysator und Stunde liegt und das Molverhältnis von Wasserstoff zu Kohlenwasserstoffen im Isomerat über 0,06 liegt.
  23. Verfahren nach einem der Ansprüche 1 bis 19, derart, dass der Isomerierungskatalysator wenigstens ein Metall der Gruppe VIII des Periodensystems der Elemente sowie einen Zeolith umfasst.
  24. Verfahren nach Anspruch 23, derart, dass dieser Zeolith gewählt ist aus der durch Mordenit und den Omega-Zeolith gebildeten Gruppe.
  25. Verfahren nach einem der Ansprüche 23 oder 24 derart, dass die Temperatur zwischen 200 und 300°C, der Wasserstoffpartialdruck zwischen 0,1 und 70 bar, die Raumgeschwindigkeit zwischen 0,5 und 10 Liter flüssiger Kohlenwasserstoffe pro Liter Katalysator und Stunde beträgt und das Molverhältnis von Wasserstoff zu Kohlenwasserstoff im Isomerat zwischen 0,07 und 15 liegt.
  26. Verfahren nach einem der Ansprüche 20 bis 25 derart, dass das Metall der Gruppe VIII gewählt ist aus der durch Platin, Nickel und Palladium gebildeten Gruppe.
  27. Verfahren nach einem der Ansprüche 1 bis 26, derart, dass der gegebenenfalls im Überschuss vorhandene Wasserstoff, der am Kopf der Destillationszone austritt, rückgewonnen, komprimiert und in der Hydrierzone wieder verwendet werden kann.
  28. Verfahren nach einem der Ansprüche 1 bis 26, derart, dass der gegebenenfalls im Überschuss vorhandene Wasserstoff, der am Kopf der Destillationszone austritt, rückgewonnen, dann komprimiert und in der Isomerierungszone wiederverwendet werden kann.
  29. Verfahren nach einem der Ansprüche 1 bis 26, derart, dass der gegebenenfalls im Überschuss vorhandene Wasserstoff, der am Kopf der Destillationszone austritt, rückgewonnen wird und dann vor den Kompressionsstufen, die einer katalytischen Reformierungseinheit zugeordnet sind, im Gemisch mit dem aus dieser Einheit kommenden Wasserstoff injiziert wird.
  30. Verfahren nach Anspruch 29, derart, dass diese Einheit der katalytischen Reformierung bei einem Druck unterhalb von 8 bar arbeitet.
  31. Verfahren nach einem der Ansprüche 1 bis 30, derart, dass man auch in der Isomerierungszone einen anderen Schnitt behandelt, welcher Paraffine umfasst, die zum größeren Teil 5 oder 6 Kohlenstoffatome pro Molekül einschließen.
EP96402910A 1995-12-27 1996-12-27 Verfahren zur Erniedrigung des Gehaltes von Benzol und von leichten ungesättigten Verbindungen in Kohlenwasserstofffraktionen Expired - Lifetime EP0781831B1 (de)

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