EP0832958B1 - Verfahren und Vorrichtung zur Erzeugung von katalytischen Krackbenzinen mit niedrigem Schwefelgehalt - Google Patents

Verfahren und Vorrichtung zur Erzeugung von katalytischen Krackbenzinen mit niedrigem Schwefelgehalt Download PDF

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EP0832958B1
EP0832958B1 EP97402088A EP97402088A EP0832958B1 EP 0832958 B1 EP0832958 B1 EP 0832958B1 EP 97402088 A EP97402088 A EP 97402088A EP 97402088 A EP97402088 A EP 97402088A EP 0832958 B1 EP0832958 B1 EP 0832958B1
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zone
cut
gasoline
light
line
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EP0832958A1 (de
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Thierry Chapus
Christian Marcilly
Blaise Didillon
Charles Cameron
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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
    • C10G67/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only
    • 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
    • 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 present invention relates to a method and an installation for the production catalytic cracking gasolines with low sulfur content.
  • the reformulated gasoline production meeting the new environmental standards notably requires that their concentration of olefins and / or aromatics (especially benzene) and sulfur (including mercaptans) be reduced.
  • Catalytic cracking gasolines have high olefin contents, and the sulfur present in the gasoline pool is attributable to nearly 90% of FCC gasoline.
  • US Patent 5,318,690 proposes a process with a fractionation of gasoline, a softening of the light fraction, while the heavy fraction is hydrodesulfurized, then converted to ZSM-5 and redesulfurized under mild conditions.
  • This technique is based on a separation of the raw gasoline so as to obtain a light cut practically free from sulfur compounds other than mercaptans, so as to treat the cut only with softening to remove the mercaptans.
  • the heavy cut contains a relatively large amount of olefins which are in saturated part during the hydrotreatment.
  • the patent advocates cracking on ZSM-5 to produce olefins, but detriment of yield.
  • these olefins can be reconstituted in the presence of H2S to form mercaptans, which has the drawback of calling a additional softening, or desulfurization.
  • Another means commonly used by the refiner to treat this problem of sulfur in gasolines is to separate the boiling fraction of at least 180 ° C which contains most of the sulfur compounds other than mercaptans. This fraction is then downgraded with the LCO (light cycle oil) and is generally not valued, or it is used as a charge diluent.
  • LCO light cycle oil
  • the applicant has sought a process for the production of low sulfur catalytic cracking, which makes it possible to efficiently conserve all of the gasoline cut, reduce the sulfur content of the gasoline cut to very low levels, without loss of gasoline yield, and minimizing octane loss.
  • the feedstock is a catalytic cracking gasoline whose boiling point range typically ranges from C5 up to 220 ° C.
  • the end point of the petrol cut depends of course on the refinery and the market constraints, but generally remains within the limits indicated above.
  • the sulfur content of these catalytic cracked gasoline (FCC) gasoline sections depends on the sulfur content of the FCC-treated feed as well as the end point of the cut. Light fractions naturally have a lower sulfur content than heavier cuts. Generally, the sulfur content of the entire gasoline cut from the FCC is greater than 100 ppm by weight and most often greater than 500 ppm by weight.
  • the sulfur contents are often greater than 1000 ppm by weight, in some cases even reaching values of the order of 4000 to 5000 ppm by weight.
  • the crude gasoline from catalytic cracking is fractionated into at least one light cut and at least one heavy cut.
  • the light cut to a final boiling point less than or equal to 210 ° C, preferably less than or equal to 180 ° C, preferably less than or equal to 160 ° C and even more preferably less than or equal to 145 ° C.
  • the light fraction of the petrol fraction contains relatively few sulfur compounds, which are predominantly in the form of mercaptans, whereas the sulfur compounds of the heavier fractions are present in the form of substituted or unsubstituted thiophenes, or of heterocyclic compounds such as benzothiophene. which, unlike mercaptans, can not be removed by extractive processes. These sulfur compounds are therefore removed by hydrotreatment.
  • the light cut is relatively rich in olefins, and the sulfur is mainly present in the form of mercaptans, while the heavier cut is relatively poor in olefins and is characterized by significantly higher sulfur contents. More generally, and contrary to the prior art, the cutting point is chosen so as to maximize the olefin content in the light cut.
  • the catalytic cracking gasoline fraction (FCC) is thus fractionated into at least two fractions, which are then subjected to different desulfurization treatments.
  • the light fraction undergoes a desulfurization treatment constituted by a hydrogenation sweet, possibly preceded by a selective hydrogenation of diolefins.
  • the Hydrogenation conditions are chosen mild to minimize the saturation of olefins of high octane number.
  • the desulfurization is not complete but it virtually eliminates all sulfur compounds other than mercaptans from so that basically remain in the cut the mercaptans. They are then removed by softening. This softening step can be a softening extraction, or catalytic oxidation softening of fixed bed mercaptans.
  • the hydrogenation of the dienes is a step which makes it possible to eliminate practically all the dienes present in the light fraction before the gentle hydrotreatment. It generally takes place in the presence of a catalyst comprising at least one Group VIII metal (and preferably Pt, Pd or Ni) and a support, at a temperature of 50-250 ° C. under a pressure of 4-50 bar. This step does not necessarily cause softening. It is particularly advantageous to operate under conditions such that at least partial softening of the gasoline is obtained, that is to say with the reduction of the mercaptan content.
  • a catalyst comprising 0.1 to 1% of palladium deposited on a support operating under a pressure of 4-25 bar, at a temperature of 50-250 ° C, with a space velocity of the liquid ( LHSV) from 1 to 10 h -1 .
  • the catalyst comprises palladium (0.1 to 1% by weight, and preferably 0.2-0.5% weight) deposited on an inert support such as alumina, silica, silica-alumina, or carrier containing at least 50% alumina.
  • an inert support such as alumina, silica, silica-alumina, or carrier containing at least 50% alumina.
  • Another metal may be combined to form a bimetallic catalyst, such as nickel (1-20% by weight, and preferably 5-15% by weight) or gold (Au / Pd expressed by weight greater than or equal to 0.1 and less than 1, and preferably between 0.2 and 0.8).
  • a bimetallic catalyst such as nickel (1-20% by weight, and preferably 5-15% by weight) or gold (Au / Pd expressed by weight greater than or equal to 0.1 and less than 1, and preferably between 0.2 and 0.8).
  • the choice of operating conditions is particularly important. We will operate the most generally under pressure in the presence of a quantity of hydrogen in small excess by relative to the stoichiometric value necessary to hydrogenate the diolefins.
  • the hydrogen and the charge to be treated are injected in ascending or descending currents in a reactor preferably with a fixed bed of catalyst.
  • the temperature is included more generally between 50 and 200 ° C, and preferably between 80 and 200 ° C, and preferably between 150 and 170 ° C.
  • the pressure is sufficient to maintain more than 80% weight, and preferably more than 95% by weight, gasoline to be treated in the liquid phase in the reactor to know the most generally between 4 and 50 bar and preferably above 10 bar.
  • a pressure is between 10-30 bar, and preferably between 12-25 bar.
  • the space velocity is in these conditions established between 1-10 h -1 , preferably between 4-10 h -1 .
  • the light fraction of the gasoline catalytic cracking fraction may contain about 1% by weight of diolefins.
  • the diolefin content is reduced to less than 3000 ppm, or even less than 2500 ppm and better still less than 1500 ppm. In some cases it can be obtained less than 500 ppm.
  • the diene content after selective hydrogenation can even be reduced to less than 250 ppm.
  • the hydrogenation step takes place in a catalytic hydrogenation reactor which comprises a catalytic reaction zone traversed by the entire charge and the amount of hydrogen necessary to effect the desired reactions.
  • the hydrogenation step takes place in a catalytic hydrogenation reactor which is arranged in a particular manner, namely at least two catalytic zones, the first being crossed by the liquid charge (and a amount of hydrogen less than the stoichiometry necessary to convert all the diolefins to mono-olefins), the second receiving the liquid charge from the first zone (as well as the rest of the hydrogen, that is to say a quantity of sufficient hydrogen to convert the remaining diolefins to mono-olefins and to at least partially isomerize the primary and secondary olefins to tertiary olefins), for example injected through a lateral tubing and dispersed using a suitable diffuser.
  • the proportion of the first zone (by volume) is at most equal to 75% of the sum of the 2 zones and preferably of 15 to 30%.
  • Another advantageous embodiment comprises hydrogenation of the dienes on a catalyst other than Pd, a mild hydrotreatment and a final oxidizing softening.
  • the gentle hydrodesulphurization of the light fraction of the FCC gasoline fraction is intended, by using a conventional hydrotreating catalyst under mild conditions of temperature and pressure, to convert the sulfur compounds of the other section into H 2 S. mercaptans, so as to obtain an effluent containing as sulfur compounds only mercaptans.
  • the cut thus produced has the same distillation range, and a slightly lower octane number due to the inevitable partial saturation of the olefins.
  • the conditions of the hydrotreatment reactor must be adjusted to achieve the desired desulfurization level, and especially to minimize the octane loss resulting from the saturation of the olefins. At least 90% of the olefins are generally converted (the diolefins being totally or substantially completely hydrogenated), and preferably at most 80-85% of the olefins are converted.
  • the temperature of the mild hydrotreating step is generally between 160 ° C and 380 ° C, preferably between 180 ° C and 360 ° C, and more preferably between 180 ° C and 320 ° C.
  • Low to moderate pressures are generally sufficient, between 5 and 50 bar, preferably between 10 and 45 bar, and more preferably between 10 and 30 bar.
  • the LHSV space velocity is between 0.5 and 10 h -1, preferably between 1 and 6 h -1.
  • the catalyst (s) used in the mild hydrotreating reactor is a conventional hydrodesulfurization catalyst, comprising at least one Group VI metal and / or at least one Group VIII metal, on a suitable support. .
  • the Group VI metal is usually molybdenum or tungsten, and the Group VIII metal is generally nickel or cobalt. Combinations such as Ni-Mo or Co-Mo are typical.
  • the catalyst support is usually a porous solid such as alumina, silica-alumina or other porous solids such as magnesia, silica or TiO2, alone. or in admixture with alumina or silica-alumina.
  • the lighter fraction of the gasoline fraction is then subjected to a non-hydrogenating desulphurization to remove the remaining sulfur compounds in the form of mercaptans.
  • a non-hydrogenating desulphurization to remove the remaining sulfur compounds in the form of mercaptans.
  • It may be an extractive softening process using sodium hydroxide or sodium or potassium cresylate. Extractive processes are sufficient as long as the processed section does not contain high molecular weight mercaptans. Softening can also be achieved by catalytic oxidation of mercaptans to disulfides.
  • This catalytic oxidation of the mercaptans to disulfides can be carried out simply by mixing the gasoline to be treated with an aqueous solution of an alkaline base, such as sodium hydroxide, in which a catalyst based on a metal chelate is added in the presence of an oxidizing agent.
  • an alkaline base such as sodium hydroxide
  • a catalyst based on a metal chelate is added in the presence of an oxidizing agent.
  • the alkaline base is not incorporated in the catalyst.
  • the metal chelate used as a catalyst is generally a metal phthalocyanine, such as cobalt phthalocyanine, for example.
  • the reaction is carried out at a pressure of between 1 and 30 bar, at a temperature of between 20 and 100 ° C, and preferably 20 and 80 ° C.
  • the alkaline base may be incorporated into the catalyst by introducing an alkaline ion into a mixed oxide structure consisting essentially of combined aluminum and silicon oxides.
  • alkali metal aluminosilicates more particularly sodium and potassium, characterized by an Si / Al atomic ratio of structure less than or equal to 5 (ie an SiO 2 / Al 2 O 3 molar ratio are used.
  • these alkali aluminosilicates have the advantage of a very low solubility in an aqueous medium, which allows their prolonged use in the hydrated state to treat petroleum fractions to which a little water is added regularly or, optionally, alkaline solution.
  • This step of softening (preferably carried out in a fixed bed) of the light gasoline fraction containing mercaptans can therefore be defined as comprising the passage, under oxidation conditions, of the gasoline to be treated (stabilized) in contact with a porous catalyst.
  • a porous catalyst Preferably, according to the patent EP-A-638,628, it comprises from 10 to 98%, preferably from 50 to 95% by weight, of at least one inorganic solid phase consisting of an alkali aluminosilicate having an Si / Si atomic ratio. Al less than or equal to 5, preferably less than or equal to 3, from 1 to 60% by weight of activated carbon, from 0.02 to 2% by weight of at least one metal chelate and from 0 to 20% by weight at least one inorganic or organic binder.
  • This porous catalyst has a basicity determined according to ASTM 2896 greater than 20 milligrams of potash per gram and a total BET surface area greater than 10 m 2 / g, and contains within its porosity a permanent aqueous phase representing 0, 1 to 40%, preferably 1 to 25%, by weight of the dry catalyst.
  • said alkali aluminosilicate is obtained by reaction in a medium aqueous solution of at least one clay (kaolinite, halloysite, montmorillonite, etc.) with at least one compound (hydroxide, carbonate, acetate, nitrate, etc.) of at least one metal alkali, in particular sodium, and potassium, this compound being preferably hydroxide, followed by a heat treatment at a temperature between 90 and 600 ° C, preferably between 120 and 350 ° C.
  • kaolinite, halloysite, montmorillonite, etc. at least one compound (hydroxide, carbonate, acetate, nitrate, etc.) of at least one metal alkali, in particular sodium, and potassium, this compound being preferably hydroxide, followed by a heat treatment at a temperature between 90 and 600 ° C, preferably between 120 and 350 ° C.
  • the clay can also be heat treated and crushed before being brought into contact with the alkaline solution.
  • kaolinite and all its thermal transformation products metalakaolin, inverse spinel phase, mullite
  • metalakaolin, inverse spinel phase, mullite can be used according to the method of the invention.
  • the clay is kaolin, kaolinite and / or metakaolin are the preferred basic chemical reagents.
  • metal chelate it will be possible to deposit on the support any chelate used for this purpose in the prior art, in particular phthalocyanines, porphyrins or metal corrines. Particularly preferred are cobalt phthalocyanine and vanadium phthalocyanine.
  • the metal phthalocyanine is preferably used in the form of a derivative thereof, with particular preference for its commercially available sulfonates, for example cobalt phthalocyanine mono- or disulfonate and mixtures thereof. this.
  • water can be added, in adequate quantity, to the cut upstream of the catalyst in a continuous or discontinuous manner to maintain the degree of hydration within the desired range, that is, the water content of the support is maintained between 0.1 and 40% by weight of the support, and preferably between 1 and 25%.
  • the temperature of the feed is set to a sufficient value, below 80 ° C, to solubilize the reaction water resulting from the transformation of mercaptans into disulfides.
  • the temperature of the charge is thus chosen so as to maintain the water content of the support between 0.1 and 40% by weight of the support and, preferably, between 1 and 25% by weight thereof.
  • This range of predetermined values of the water content of the support will, of course, depend on the nature of the catalyst support used in the softening reaction.
  • this softening step can be eliminated when the light cut has been selectively hydrogenated to remove dienes and at the same time softening has been achieved.
  • the sweetening yield may be such that the final softening step with an oxidizing agent may no longer be necessary.
  • This case is true with a catalyst based on palladium as described above.
  • the presence of this treatment step with a palladium catalyst can also make it possible to modify the softening step, for example by increasing the hourly speed, hence increasing productivity, or reducing the amount of catalyst, hence a reduced investment.
  • a step of selective hydrogenation of the dienes can be used which is not softening.
  • Hydrodesulfurization of the heaviest fraction of FCC gasoline is conducted following the same process as that used for the light fraction.
  • the catalyst contains also at least one metal of G VIII and / or group VI, deposited on a support. Only the operating conditions are adjusted, in order to obtain the level of desulfurization desired, on this cup richer in sulfur.
  • the temperature used is usually between 200 ° C and 420 ° C, preferably between 220 ° C and 400 ° C.
  • the pressures operating procedures are generally between 20 and 80 bar and preferably between 30 and 50 bar. The effluent obtained is stripped to eliminate H2S and is sent to the pool petrol.
  • the softening zone is located after the stripping and the installation further comprises a zone for selective hydrogenation of the dienes located between the fractionation column and the soft hydrotreating zone, said hydrogenation zone comprising a driving for the introduction of the light cut and driving for the release of the light cut dedienized.
  • the plant also comprises a zone (15) for hydrotreating the heavy fraction, provided with a pipe (4) for introducing the heavy cut from the column (1), a pipe ( 16) for the outlet of the hydrotreated section and a line (17) supplying the hydrogen at the charge or the zone, said zone being followed by a stripping column (18) provided with a pipe for the introducing the hydrotreated cut, a pipe (19) for the outlet of H 2 S and a pipe (20) for the outlet of the hydrotreated cut.
  • the cuts leaving the pipes (20) and (13) can be sent to the fuel storage via a pipe (21).
  • Example 1 illustrates a process without a softening step on Pd
  • the following example illustrates the process, in the case where the crude gasoline cut is fractionated into a light C5 cut less than 80 ° C, and a heavier fraction 180-220 ° C.
  • Table 1 shows the characteristics of these different sections. Characteristics of the different FCC petrol cuts Chopped off Total gasoline (C5-220 ° C) Light fraction (C5-180 ° C) Heavy fraction (180-220 ° C) (% wt) (100) (70) (30) Olefin content (% wt) 44.0 56.4 10.0 Aromatic content (% wt) 23.0 4.6 66.0 Bromine index 68 90 16 Total sulfur (ppm wt) 200 154 307 Sulfur mercaptans (ppm wt) 106 74 0 RON 92.0 92.5 90.8 MY 80.0 80.7 78.4 (RON + MON) / 2 86.0 86.6 84.6
  • the light cut of FCC gasoline is rich in olefins and contains almost all mercaptans.
  • the heavier fraction which is richer in sulfur, contains sulfur compounds essentially in the form of thiophene derivatives.
  • Table 2 below indicates the operating conditions used for the hydrotreatment of heavy gasoline, as well as the characteristics of the heavy gasoline thus desulfurized.
  • the catalyst used is a CoMo supported alumina (HR 306C sold by the company Procatalyse). Characteristics of hydrodesulfurization of heavy gasoline.
  • Table 3 below indicates the characteristics of the light gasoline desulfurized and softened.
  • the temperature is 280 ° C.
  • the pressure is 20 bar
  • the LHV is 8 h -1
  • the catalyst is the NiMo-based LD 145 sold by Procatalyse followed by CoMo catalyst (HR306 C sold by the company Procatalyse). Characteristics of the initial light gasoline, after mild hydrotreatment and then after softening.
  • the softening is performed on a catalyst comprising sodalite (alkali aluminosilicate) and 20% of activated carbon, impregnated with an oxidizing agent such as sulfated cobalt phthalocyamine (impregnation of PeCo: 60 kg (m 3 of cata) prepared such that described in EP-A-638,628).
  • an oxidizing agent such as sulfated cobalt phthalocyamine (impregnation of PeCo: 60 kg (m 3 of cata) prepared such that described in EP-A-638,628).
  • the method and the installation according to the invention thus make it possible to obtain FCC containing less than 50 ppm sulfur, responding negatively to the "doctor test" and this with a loss in octane number barrel (RON + MON) / 2 lower than 8 points per compared to the same raw gasoline fraction of FCC before treatment, and preferably less than or equal to 6 points.

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Claims (10)

  1. Verfahren zur Herstellung eines gesüßten Benzins, das weniger als 50 ppm Schwefel enthält aus Rohbenzin von katalytischem Cracken, das Olefine, Mercaptane und schwefelhaltige Verbindungen enthält, die von Mercaptanen verschieden sind, in welchen Verfahren:
    1) das Rohbenzin zu wenigstens einer leichten Fraktion mit Endsiedepunkt unter oder gleich 210°C fraktioniert wird, die den Hauptteil der Olefine und der Mercaptane enthält, und wenigstens einer schweren Fraktion, wobei die Fraktionen anschließend verschiedenen Entschwefelungsbehandlungen unterzogen werden,
    2) die leichte Fraktion einem weichen Hydrotreatment in Gegenwart von Wasserstoff mit einem Katalysator unterzogen wird, der wenigstens ein Metall der Gruppe VIII und/oder wenigstens ein Metall der Gruppe VI enthält, bei einer Temperatur von 160 bis 380°C unter einem Druck von 10 bis 30 bar und der erhaltene Abstrom abgestreift wird, um H2S zu entfernen,
    3) die leichte Fraktion einem Süßen wenigstens teilweise unterzogen wird und einer Hydrierung der Diene durch Behandlung der leichten Fraktion vor dem weichen Hydrotreatment in Gegenwart von Wasserstoff mit einem Katalysator, der 0,1 bis 1% Palladium, abgeschieden auf einem Träger, enthält, bei einer Temperatur von 50 bis 250°C, unter einem Druck von 4 bis 25 bar mit einer stündlichen Raumgeschwindigkeit der Flüssigkeit von 1 bis 10 h-1,
    4) die schwere Fraktion einem Hydrotreatment in Gegenwart von Wasserstoff mit einem Katalysator unterzogen wird, der wenigstens ein Metall der Gruppe VI und/oder wenigstens ein Metall der Gruppe VIII enthält, bei einer Temperatur von 200 bis 420°C und einem Druck von 20 bis 80 bar und der erhaltene Abstrom abgestreift wird, um H2S zu entfernen.
  2. Verfahren nach Anspruch 1, in welchem die leichte Fraktion vor dem weichen Hydrotreatment der selektiven Hydrierung der Diene unterzogen wird und die hydrierbehandelte und abgestreifte Fraktion einem Süßen unterzogen wird, das durch eines der folgenden Verfahren durchgeführt wird:
    extraktives Süßen des Abstroms, der nach weichem Hydrotreatment und Abstreifen erhalten wird;
    Süßen mit einem Oxidationsmittel, einem Katalysator und einer Alkalibase, die gegebenenfalls in den Katalysator einverleibt ist, des Abstroms, der nach weichem Hydrotreatment und Abstreifen erhalten ist.
  3. Verfahren nach einem der vorhergehenden Ansprüche, bei dem die leichte Fraktion einen Endsiedepunkt unterhalb oder gleich 180°C aufweist.
  4. Verfahren nach einem der vorhergehenden Ansprüche, bei dem die leichte Fraktion einen Endsiedepunkt unterhalb oder gleich 160°C aufweist.
  5. Verfahren nach einem der vorhergehenden Ansprüche, bei dem die leichte Fraktion einen Endsiedepunkt unterhalb oder gleich 145°C aufweist.
  6. Verfahren nach einem der vorhergehenden Ansprüche, bei dem die Behandlung der leichten Fraktion vor weichem Hydrotreatment mit einem Katalysator durchgeführt wird, der 0,1 bis 1 Palladium und 1 bis 20 Gew.-% Nickel enthält.
  7. Verfahren nach einem der vorhergehenden Ansprüche, bei dem die Behandlung der leichten Fraktion vor dem weichen Hydrotreatment mit einem Katalysator durchgeführt wird, der 0,1 bis 1% Palladium und Gold in einem Gewichtsverhältnis Au/Pd von wenigstens 0,1 und unter 1 enthält.
  8. Verfahren nach einem der vorhergehenden Ansprüche, bei dem das extraktive Süßen mit einem Oxidationsmittelreagens bei 20 bis 100°C unter einem Druck von 1 bis 30 bar durchgeführt wird.
  9. Anlage zur Erzeugung von Benzinen mit geringem Schwefelgehalt aus Benzin von katalytischem Kracken, umfassend:
    eine Kolonne (1) zur Fraktionierung, ausgerüstet mit einer Leitung (2) zum Einführen des Rohbenzins, das von dem katalytischen Kracken kommt, und wenigstens zwei Leitungen umfassend, die eine (3) in dem oberen Teil der Kolonne für den Austritt der leichten Fraktion und die andere (4) in dem unteren Teil der Kolonne für den Austritt der schweren Fraktion;
    eine Zone (5) zum Hydrotreatment in Gegenwart von Wasserstoff, die ein katalytisches Bett mit einem Katalysator umfasst, der wenigstens ein Metall der Gruppe VIII und/oder wenigstens ein Metall der Gruppe VI enthält, eine Leitung (6) zum Eintritt der leichten zu behandelnden Benzinfraktion, wobei die Leitung mit der Zone zur Behandlung (7) auf Palladiumkatalysator verbunden ist, wobei die Hydrotreatmentzone auch eine Leitung (8) zum Austritt des hydrierbehandelten Abstroms umfasst,
    eine Zone (9) zum Abstreifen, umfassend eine Leitung zum Einführen von leichtem hydrierbehandelten Benzin, eine Leitung (10) zur Entfernung von H2S und eine Leitung (11) zum Austritt des leichten abgestreiften Benzins,
    und wobei die Anlage auch umfasst:
    eine Zone (7) zum Süßen und zum Hydrieren der Diene, angeordnet vor der Hydrotreatmentzone und eine Leitung (3) umfassend zur Einführung der leichten Benzinfraktion aus der Fraktionierungskolonne, eine Leitung zum Austritt der leichten behandelten Benzinfraktion, wobei die Zone auch wenigstens ein Katalysatorbett mit 0,1 bis 1% Palladium, abgeschieden auf einem Träger umfasst und die Anlage außerdem eine Leitung (13) zum Austritt des leichten abgestreiften und gesüßten Benzins aus der Anlage heraus umfasst, die mit der Zone (12) oder der Zone (9) verbunden ist,
    eine Zone (15) zum Hydrotreatment der schweren Fraktion mit einem Katalysator, der wenigstens ein Metall der Gruppe VI und/oder wenigstens ein Metall der Gruppe VIII enthält, ausgerüstet mit einer Leitung (4) zum Einführen der schweren Fraktion, die von der Kolonne kommt, eine Leitung (16) für den Austritt der hydrierbehandelten Fraktion und eine Leitung (17), die Wasserstoff auf der Ebene der Beschickung oder der Zone zuführt, wobei die Zone von einer Kolonne (18) zum Abstreifen gefolgt ist, ausgerüstet mit einer Leitung zur Einführung der hydrierbehandelten Fraktion, einer Leitung (19) für den Austritt von H2S und einer Leitung (20) für den Austritt der hydrierbehandelten Fraktion.
  10. Anlage nach Anspruch 9, außerdem umfassend eine Zone (12) zum Süßen, angeordnet nach der Zone zum Abstreifen, umfassend eine Leitung zum Einführen von leichtem abgestreiften Benzin und eine Leitung (14) zur Zufuhr von Oxidationsmittelreagens auf dem Niveau dieser Zone.
EP97402088A 1996-09-24 1997-09-08 Verfahren und Vorrichtung zur Erzeugung von katalytischen Krackbenzinen mit niedrigem Schwefelgehalt Expired - Lifetime EP0832958B1 (de)

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FR9611691A FR2753717B1 (fr) 1996-09-24 1996-09-24 Procede et installation pour la production d'essences de craquage catalytique a faible teneur en soufre
FR9611691 1996-09-24

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KR19980024831A (ko) 1998-07-06
US6838060B1 (en) 2005-01-04
DE69733985D1 (de) 2005-09-22
EP0832958A1 (de) 1998-04-01
JP4006483B2 (ja) 2007-11-14
FR2753717A1 (fr) 1998-03-27
KR100456209B1 (ko) 2005-01-27
JPH10102070A (ja) 1998-04-21
US6007704A (en) 1999-12-28
DE69733985T2 (de) 2006-01-26

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