EP1700899B1 - Procédé d'hydrocraquage avec recyclage comprenant l'adsorption de composés polyaromatiques de la fraction recyclée sur un adsorbant à base de silice-alumine à teneur limitée en macropores - Google Patents

Procédé d'hydrocraquage avec recyclage comprenant l'adsorption de composés polyaromatiques de la fraction recyclée sur un adsorbant à base de silice-alumine à teneur limitée en macropores Download PDF

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EP1700899B1
EP1700899B1 EP06290332A EP06290332A EP1700899B1 EP 1700899 B1 EP1700899 B1 EP 1700899B1 EP 06290332 A EP06290332 A EP 06290332A EP 06290332 A EP06290332 A EP 06290332A EP 1700899 B1 EP1700899 B1 EP 1700899B1
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hydrocracking
process according
adsorbent
measured
adsorption
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French (fr)
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EP1700899A1 (fr
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Karin Barthelet
Patrick Euzen
Hugues Dulot
Patrick Bourges
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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
    • C10G67/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only
    • C10G67/06—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one process for refining in the absence of hydrogen only plural serial stages only including a sorption process as the refining step in the absence of hydrogen
    • 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
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4081—Recycling aspects
    • 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
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4093—Catalyst stripping

Definitions

  • the invention relates to the elimination of polyaromatic compounds (PNA) in the field of hydrocracking processes.
  • PNA polyaromatic compounds
  • a hydrocracking process is a heavy charge conversion process (higher boiling point of hydrocarbons, generally at 380 ° C) from vacuum distillation. It operates at high temperature and under high pressure of hydrogen and makes it possible to obtain products of very good quality because rich in paraffinic and naphthenic compounds and with very few impurities.
  • this method has several drawbacks: it is, by its hydrogen consumption, expensive and it does not have a very high yield (30 to 40% of the unconverted load). It seems interesting to set up a recycling loop. Nevertheless, this recycling leads to an accumulation of polyaromatic compounds (called PNA) which are formed during the passage of the feedstock over the hydrocracking catalyst and ultimately to the formation of coke on the same catalyst.
  • PNA polyaromatic compounds
  • the polyaromatic molecules 1 are molecules consisting of an assembly of aromatic rings (presence also possible of one or more saturated rings), substituted or not by alkyl groups. Because of their high molecular weight, they are very low volatility compounds and often solid at room temperature. Finally, their strong aromaticity and the absence of polar substituents on the rings lead to a very low solubility of these molecules in water or in alkanes. This solubility decreases further when the number and length of the alkyl side chains become lower. 1 Julius Scherzer; AJGruia Hydrocracking Science and Technology, Marcel Dekker Inc .: New York, 1996; Chapter 11, pp 200-214 .
  • NAPs are sometimes classified into several categories according to their number of nuclei: light PNAs with 2 to 6 nuclei, heavy PNAs containing 7 to 10 nuclei and finally NAPs with cycles greater than 11. It is generally accepted that the hydrocracker inlet feedstocks mainly contain light PNA. After passing over the hydrocracking catalyst, one observes on the one hand a higher concentration of these molecules but also the presence of heavy PNA which are the most harmful molecules for the hydrocracking process (deposition on the catalyst and in the unit / precursors for coke formation). These can be formed either by condensation of two or more light PNAs, or by dehydrogenation of larger polycyclic compounds, or by cyclization of the pre-existing side chains on PNA followed by dehydrogenation. Subsequently reactions of combinations or dimerizations of heavy PNA can take place resulting in the formation of compounds with more than 11 nuclei.
  • NAPs For the detection and analysis of NAPs, several options are possible 2 . However, since they are often mixtures of PNA, it is preferable to separate the different molecules beforehand. For this purpose, liquid chromatography (HPLC) is used. Then, detection, identification and determination of PNA can be done either by UV absorption or by fluorescence. These are specific NAP methods and therefore sensitive, but they do not always detect all NAPs (average quantitative reliability). Direct analyzes by mass spectrometry or IR are also possible but they are more difficult to implement and exploit. 2 Milton L. Lee; Milos V.Novotny; Keith D.Bartle Analytical Chemistry of Polycyclic Aromatic Compounds; Academic Press, Inc .: London, 1981 .
  • the precipitation of PNA is caused by the addition of flocculent (patent US5,232,577 ) and / or a drop in temperature (patent US 5,120,426 ) and is followed by decantation or centrifugation and phase separation.
  • This is an effective technique but which seems unsuitable for a hydrocracking process operating continuously because of the high residence times required either for the precipitation itself or for the decantation of PNA and the probable crystallization of paraffins at low temperatures applied.
  • Adsorption is an effective method which, depending on the solid and the operating conditions chosen, is compatible with a hydrocracker operating continuously. In fact, it is the most frequently considered solution, as shown by the large number of patents filed on this subject. They cover several process configurations.
  • the adsorption zone may be put in place either before or after the hydrocracker. In the first case, it is a matter of pre-treating the load ( US 4,775,460 ) and eliminate the PNA precursors. Nevertheless, since NAPs are mainly formed during passage over the hydrocracking catalyst, the interest of this solution is limited. It is, on the contrary, useful to seek to reduce or even eliminate the PNA of the fraction that will be recycled on the catalyst to prevent these molecules from growing and accumulating.
  • the adsorption zone and in particular the nature of the adsorbent is more or less detailed.
  • all known conventional adsorbents are mentioned: silica gel, activated charcoal, activated or non-activated alumina, silica gel / alumina, clay, polystyrene gel, cellulose acetate, molecular sieve (zeolite).
  • zeolite molecular sieve
  • the most suitable ones seem to be activated carbons, aluminas and amorphous silicas.
  • the selected solids should have a pore volume, a BET surface and the largest possible pore diameter.
  • the exit effluent once cooled to 16-49 ° C, is then sent to a liquid-vapor separator and the liquid recovered in a distillation column to separate the mono compounds from the polyaromatic compounds.
  • the liquid desorbent it must have a certain affinity with the solid to be able to displace the PNAs and with the PNAs to solubilize them.
  • the best solvents are therefore aromatic compounds alone (toluene, benzene, ethylbenzene, cumene, xylenes) or mixed (light cuts from the FCC reactor) ( US 5,124,023 ).
  • Other types of solvents such as hydrocarbon-halogenated solvents, ketones, alcohols or light hydrocarbons alone or as a mixture ( US 4,732,665 ) were also mentioned.
  • Adsorption seems to be the most suitable solution for the removal of NAPs in a hydrocracking unit, the optimum positioning of this purification zone being that at the outlet of the distillation tower. This is confirmed by the fact that only this solution has been implemented industrially 3 .
  • the disadvantage of this method is that it does not provide regeneration of activated carbon and therefore has a high cost. 3 Stuart Frazer; Warren Berry PTQ 1999, 632, 25-35 .
  • activated carbons are the solids with the largest adsorption capacities, they can currently be regenerated only by solvent elution. In addition to the fact that the amount of solvent required is very important, it would be necessary to set up an additional separation system to recycle the solvent. This solution would be much too expensive to implement. In the context of a refinery, the ideal solution would be to regenerate solids by burning. This technique is not applicable to activated carbons. It was therefore a question of identifying sufficiently strong solids with respect to active carbons but more resistant than these.
  • the solid adsorbent must be capable of retaining selectively and in large amounts the PNA with a selectivity greater than 1 and preferably between 2 and 5 for the coronene compared to other lesser PNA such as pyrene (4 aromatic nuclei) or perylene (5 aromatic nuclei).
  • the porosity of the adsorbent it is necessary that it has free openings (taking into account the Van der Waals radii of the atoms pointing towards the center of the pore) of pores greater than 11.4 ⁇ (calculations from the literature considering a plane molecule with 1.395 ⁇ for DC, 1.084 ⁇ for CH and 1.2 ⁇ for the van der Waals radius of hydrogen 4 ) and preferably greater than 20 ⁇ .
  • This condition excludes so-called microporous solids such as zeolites since the faujasite which is the zeolite with larger pores has tunnels opening 7.4 ⁇ .
  • the pore openings must not be too wide in order to prevent the specific surface, the pore volume and therefore the total adsorption capacity from becoming too small.
  • the specific surface must generally be greater than 200 m 2 / g and preferably greater than 400 m 2 / g. This explains why silica gels and aluminas which often have a BET surface area of less than 200 m 2 / g, are not suitable for PNA adsorption.
  • the solids that seem most suitable for the adsorption of NAPs with the exception of activated carbons are the amorphous mesoporous silica-aluminas. Although having porous volumes, specific surfaces and therefore adsorption capacities weaker than activated carbons, they have the advantage of being prepared at high temperature and therefore of being resistant to burning. 4 Henry W. Haynes, Jr .; Jon F.Parcher; Norman E. Heimer Ind.Eng.Chem.Process Des.Dev. 1983, 22, 409 .
  • the present invention provides an improved hydrocracking process having a step of removing polyaromatic compounds from at least a portion of the adsorption-recycled fraction on a silica-alumina adsorbent which has good adsorption capacities because of its large specific surface and its pores of sufficient size to be accessible to molecules with more than 4 nuclei.
  • This invention therefore makes it possible to effectively eliminate the PNA from the charge while offering the possibility of using the same adsorbent for several cycles because of its regenerability by burning.
  • these solids have the advantage of being denser than activated carbons which partially offsets their lower adsorption capacity adsorbent iso-mass. In addition to the gain in consumption of solid, this avoids additional investments such as the establishment of a distillation column necessary in the case of solvent regeneration.
  • the adsorbent undergoes a regeneration treatment by burning after the adsorption step.
  • the adsorption step can be performed on all or only a portion of the recycled fraction and can operate continuously or discontinuously. Preferably, the adsorption step is performed on the entire recycled fraction.
  • fillers can be processed by the hydrocracking processes described below and generally contain at least 20% by volume and often at least 80% by volume of compounds boiling above 340 ° C.
  • the feedstock may be, for example, LCOs (light cycle oil - light gas oils from a catalytic cracking unit), atmospheric distillates, vacuum distillates, for example gas oils derived from the direct distillation of the crude or from conversion units such as FCC, coker or visbreaking, as well as feedstocks from aromatics extraction units of lubricating oil bases or from solvent dewaxing of lubricating oil bases, or process distillates.
  • LCOs light cycle oil - light gas oils from a catalytic cracking unit
  • atmospheric distillates for example gas oils derived from the direct distillation of the crude or from conversion units such as FCC, coker or visbreaking, as well as feedstocks from aromatics extraction units of lubricating oil bases or from solvent dewaxing of lubricating oil bases, or process distillates.
  • the feeds have a boiling point T5 greater than 340 ° C., and more preferably greater than 370 ° C., ie 95% of the compounds present in the feed have a boiling point greater than 340. ° C, and more preferably above 370 ° C.
  • the nitrogen content of the feedstocks treated in the hydrocracking processes is usually greater than 500 ppm, preferably between 500 and 10,000 ppm by weight, more preferably between 700 and 4000 ppm by weight and even more preferably between 1000 and 4000. ppm.
  • the sulfur content of the feedstocks treated in the hydrocracking processes is usually between 0.01 and 5% by weight, preferably between 0.2 and 4% and even more preferably between 0.5 and 2%.
  • the charge may optionally contain metals.
  • the cumulative nickel and vanadium content of the feeds treated in the hydrocracking processes is preferably less than 1 ppm by weight.
  • the asphaltene content is generally less than 3000 ppm, preferably less than 1000 ppm, even more preferably less than 200 ppm.
  • the feedstock contains resins and / or asphaltenes-type compounds
  • the catalysts or guard beds used are in the form of spheres or extrudates. It is however advantageous that the catalyst is in the form of extrudates with a diameter of between 0.5 and 5 mm and more particularly between 0.7 and 2.5 mm.
  • the shapes are cylindrical (which can be hollow or not), cylindrical twisted, multilobed (2, 3, 4 or 5 lobes for example), rings.
  • the cylindrical shape is preferably used, but any other shape may be used.
  • the guard catalysts may, in another preferred embodiment, have more particular geometric shapes in order to increase their void fraction.
  • the void fraction of these catalysts is between 0.2 and 0.75.
  • Their outer diameter can vary between 1 and 35 mm.
  • hollow cylinders hollow rings, Raschig rings, serrated hollow cylinders, crenellated hollow cylinders, pentaring carts, multi-hole cylinders, etc.
  • These catalysts may have been impregnated with an active phase or not.
  • the catalysts are impregnated with a hydro-dehydrogenation phase.
  • the CoMo or NiMo phase is used.
  • the guard beds can be marketed by Norton- Saint-Gobain, for example the MacroTrap® guard beds.
  • Guard beds can be marketed by Axens in the ACT family: ACT077, ACT935, ACT961 or HMC841, HMC845, HMC941 or HMC945.
  • the catalysts having the highest void content are preferably used in the first catalytic bed or first catalytic reactor inlet. It may also be advantageous to use at least two different reactors for these catalysts.
  • the preferred guard beds according to the invention are HMC and ACT961.
  • the hydrocracking / hydroconversion or hydrotreating catalyst is generally brought into contact, in the presence of hydrogen, with the charges described above, at a temperature above 200 ° C., often between 250 and 480 ° C., advantageously between 320 and 450 ° C, preferably between 330 and 435 ° C, under a pressure greater than 1 MPa, often between 2 and 25 MPa, preferably between 3 and 20 MPa, the space velocity being between 0.1 and 20h - 1 and preferably 0.1-6h -1 , preferably 0.2-3h -1 , and the amount of hydrogen introduced is such that the volume ratio by liter of hydrogen / liter of hydrocarbon is between 80 and 5000l / l and most often between 100 and 2000 I / I.
  • the hydrocracking / hydroconversion processes using the catalysts according to the invention cover the pressure and conversion domains ranging from mild hydrocracking with high pressure hydrocracking.
  • Mild hydrocracking is understood to mean hydrocracking leading to moderate conversions, generally less than 40%, and operating at low pressure, generally between 2 MPa and 6 MPa.
  • the hydrocracking catalyst can be used alone, in one or more fixed bed catalytic beds, in one or more reactors, in a so-called one-step hydrocracking scheme, with or without liquid recycling of the unconverted fraction, optionally in combination with a hydrorefining catalyst located upstream of the hydrocracking catalyst.
  • the hydrocracking catalyst may be used alone, in one or more bubbling bed reactors, in a so-called one-step hydrocracking scheme, with or without liquid recycling of the unconverted fraction, optionally in combination with a catalyst of hydrorefining located in a fixed bed reactor or bubbling bed upstream of the hydrocracking catalyst.
  • the bubbling bed operates with removal of spent catalyst and daily addition of new catalyst to maintain stable catalyst activity.
  • the hydrocracking catalyst may be used in one or both reactors in association or not with a hydrorefining catalyst located upstream of the hydrocracking catalyst.
  • the so-called hydrocracking in one step, comprises firstly and in a general manner advanced hydrorefining which aims to carry out a hydrodenitrogenation and hydrodesulphurization of the feed before it is sent to the hydrocracking catalyst proper , especially in the case where it comprises a zeolite.
  • This extensive hydrorefining of the feed leads only to a limited conversion of the feedstock into lighter fractions, which remains insufficient and must therefore be completed on the more active hydrocracking catalyst.
  • no separation occurs between the two types of catalysts. All of the effluent at the outlet of the reactor is injected onto the hydrocracking catalyst proper and only then is separation of the products formed carried out.
  • This version of the hydrocracking also called “Once Through” has a variant that has a recycling of the unconverted fraction to the reactor for further conversion of the charge. also an incomplete separation of the ammonia effluent leaving the first zone. This separation is advantageously carried out by means of an intermediate hot flash.
  • the hydrocracking performed in the second reaction zone is carried out in the presence of ammonia in an amount less than the amount present in the feed, preferably less than 1500 ppm by weight, more preferably less than 1000 ppm by weight and even more preferably lower. at 800 ppm weight of nitrogen.
  • the hydrocracking catalyst is preferably used in the hydrocracking reaction zone in association or not with a hydrorefining catalyst located upstream of the hydrocracking catalyst.
  • the hydrocracking catalyst may be used upstream or downstream of the zeolite catalyst. Downstream of the zeolite catalyst, it makes it possible in particular to convert the PNAs or the PNA precursors.
  • the hydrocracking catalyst can be used either in the first reaction zone in pretreatment converting, alone or in combination with a conventional hydrorefining catalyst, upstream of the hydrocracking catalyst, in one or more catalytic beds, in one or more reactors.
  • the proportion of the catalytic volume of hydrorefining catalyst generally represents 20 to 45% of the total catalytic volume.
  • the effluent from the first reaction zone is at least partly, preferably completely, introduced into the second reaction zone of said process.
  • An intermediate separation of the gases can be carried out as previously described.
  • silica-alumina-based catalyst is used upstream of a zeolitic hydrocracking catalyst, for example based on zeolite Y
  • a catalyst having a high silica content by weight with silica weight contents of the support entering the catalyst composition of between 20 and 80% and preferably between 30 and 60%.
  • a hydrorefining catalyst the latter being located upstream of the hydrocracking catalyst.
  • the conversion is generally (or preferably) less than 50% by weight and preferably less than 40%.
  • the hydrocracking catalyst may be used upstream or downstream of the zeolite catalyst. Downstream of the zeolite catalyst, it makes it possible to crack the PNA.
  • the hydrocracking catalyst may be used alone in one or more reactors.
  • the bubbling-bed reactor (s) containing the hydrocracking catalyst being preceded by one or more reactors containing at least one hydrorefining catalyst. in fixed bed or bubbling bed.
  • the conversion of the fraction of the feed caused by this hydrorefining catalyst is generally (or preferably) less than 30% by weight and preferred way less than 25%.
  • the silica-alumina-based catalyst may also be used in a one-step hydrocracking process comprising a hydrorefining zone, a zone allowing the partial elimination of the ammonia, for example by a hot flash, and a zone comprising a hydrocracking catalyst.
  • This process for the hydrocracking of hydrocarbon feeds in one step for the production of middle distillates and optionally of oil bases comprises at least a first reaction zone including hydrorefining, and at least a second reaction zone, in which hydrocracking is carried out. at least a part of the effluent of the first reaction zone.
  • This process comprises
  • the effluent leaving the second reaction zone is subjected to a so-called final separation (for example by atmospheric distillation optionally followed by vacuum distillation), so as to separate the gases.
  • a so-called final separation for example by atmospheric distillation optionally followed by vacuum distillation
  • At least one residual liquid fraction is obtained, essentially containing products whose boiling point is generally greater than 340 ° C., which may be at least partly recycled upstream of the second reaction zone of the hydrocracking process, and preferably upstream of the hydrocracking catalyst based on alumina-silica, with a view to producing middle distillates.
  • the conversion to products having boiling points below 340 ° C, or even lower than 370 ° C is at least 50% by weight.
  • the two-stage hydrocracking comprises a first step whose objective, as in the "one-step” process, is to perform the hydrorefining of the feedstock, but also to achieve a conversion of the latter of the order in general. from 40 to 60%.
  • the effluent from the first step then undergoes separation (distillation), which is often called intermediate separation, which aims to separate the conversion products from the unconverted fraction.
  • separation distillation
  • intermediate separation which aims to separate the conversion products from the unconverted fraction.
  • the second step of a two-stage hydrocracking process only the fraction of the unconverted feedstock in the first step is processed. This separation allows a two-stage hydrocracking process to be more selective in middle distillate (kerosene + diesel) than a one-step process.
  • the intermediate separation of the conversion products avoids their "over-cracking" in naphtha and gas in the second step on the hydrocracking catalyst.
  • the unconverted fraction of the feedstock treated in the second stage generally contains very low levels of NH 3 as well as organic nitrogen compounds, generally less than 20 ppm by weight or less than 10 ppm. weight.
  • the same configuration of fixed bed or bubbling bed catalytic beds can be used in the first step of a so-called two-stage scheme, whether the catalyst is used alone or in combination with a conventional hydrorefining catalyst.
  • the hydrocracking catalyst may be used upstream or downstream of the zeolite catalyst. Downstream of the zeolite catalyst, it makes it possible in particular to convert the PNAs or the PNA precursors.
  • the preferred hydrocracking catalysts are doped catalysts based on non-noble group VIII elements, even more preferably nickel and tungsten base and the preferred doping element being phosphorus.
  • the catalysts used in the second stage of the two-stage hydrocracking processes are preferably the noble group-based doped catalysts, more preferably the platinum and / or palladium catalysts and the preferred doping element being phosphorus.
  • Step 2 separation of the different cuts in a distillation tower
  • This step consists in separating the effluent from the hydrocracking reactor into different petroleum fractions. After separating the liquid and gaseous streams through high and medium pressure separators, the liquid effluent is injected into an atmospheric distillation column in order to separate and stabilize the sections at desired distillation intervals.
  • the unconverted fraction which is desired to be treated in the present invention is then obtained in the bottom of an atmospheric distillation column, more specifically in the withdrawal of the reboiler, and corresponds according to the present invention to a fraction of cutting point T05 greater than 340 °. vs.
  • the polyaromatic compounds that the present invention proposes to eliminate are all concentrated in this heavy fraction from the bottom of the column of the distillation tower (heavy residue ).
  • the unconverted portion (having a boiling point greater than 340 ° C) is generally at least partially recycled and reinjected either at the inlet hydrorefining catalyst, either at the inlet of the hydrocracking catalyst (preferably).
  • the unconverted part (having a boiling point greater than 340 ° C.) is generally at least partially recycled and reinjected into the second hydrocracking reaction zone.
  • Step 3 adsorption of the PNA contained in the heavy residue by passing some or all of it in the adsorption zone
  • This step consists in eliminating all or part of the polyaromatic compounds contained in all or part of the recycled fraction from the bottom of the distillation tower column (fraction 380+ or heavy residue), that is to say
  • the objective is to maintain the content of polyaromatic compounds below a certain critical concentration beyond which there would be a deactivation of the hydrocracking catalyst (deactivation due to accumulation of PNA in the network porous hydrocracking catalyst can cause poisoning of active sites and / or blocking access to these sites) and a deposit on the cold parts of the process. It is therefore a question of controlling the concentration of PNA in the fraction recycled to the hydrocracking catalyst. Depending on the case, it is therefore possible to limit the load volumes to be treated and thus to minimize the cost of the overall process.
  • the unconverted feedstock derived from the hydrocracker is placed at least in part in contact with a solid adsorbent which is generally capable of selectively and significantly retaining the PNAs with a selectivity greater than 1 and preferably between 2 and 5 for the coronene compared to other, less heavy PNAs such as pyrene (4 aromatic rings) or perylene (5 aromatic rings).
  • a solid adsorbent which is generally capable of selectively and significantly retaining the PNAs with a selectivity greater than 1 and preferably between 2 and 5 for the coronene compared to other, less heavy PNAs such as pyrene (4 aromatic rings) or perylene (5 aromatic rings).
  • the total weight content of zeolite in the adsorbent is generally between 0% and 30%, advantageously between 0.2% and 25%, preferably between 0.3% and 20%, very preferably between 0.5%. and 20% and even more preferably between 1% and 10%.
  • the X-ray diffraction pattern of the adsorbent also generally contains the main characteristic lines of the selected zeolite or zeolites.
  • the adsorbent may also contain a minor proportion of at least one stabilizing element selected from the group consisting of zirconia and titanium.
  • the adsorbent is subjected to a hydrothermal treatment after the synthesis.
  • the adsorbent is subjected to a sulfurization treatment, according to any technique known to those skilled in the art.
  • the adsorbent does not comprise zeolite.
  • the adsorbent may be identical to the catalyst used in the hydrocracking zone.
  • the adsorbent may be a regenerated hydrorefining or hydrocracking catalyst.
  • the adsorption zone may be designed in various ways: it may consist of one or more fixed beds of adsorbents positioned in series or in parallel.
  • the operating conditions are generally a temperature of between 50 and 250 ° C., preferably of between 100 and 150 ° C., a pressure of between 1 and 200 bar (according to one embodiment of the invention).
  • the pressure is between 1 and 10 bar and according to another preferred embodiment, the pressure is between 30 and 200 bars) and a VVH between 0.01 and 500 h -1 , preferably between 0.1 and 300, terminals included.
  • the choice of temperature and pressure is made in order to ensure a good flow of the load (it must be liquid and viscosity not too high) and a good diffusion of the PNA in the porosity of the adsorbent while optimizing the adsorption phenomenon.
  • the contents of polyaromatic compounds in the feedstock to be recycled are generally between 0 and 500 ppm for coronene, from 0 and 5000 ppm for perylene and for pyrene. At the outlet of the adsorption zone, the contents generally become less than 40, 1000, 1500 ppm, respectively.
  • the determination of the molecules is carried out by liquid chromatography combined with detection by UV absorption.
  • Step 4 regeneration of the adsorbent of the adsorption zone by burning
  • This step aims to eliminate the PNA previously adsorbed on the solid of the adsorption zone (step 3) so as to make it reusable for a new adsorption step.
  • Regeneration of the adsorbent by burning is carried out under an N 2 -based gas stream containing from 0.1 to 21% of O 2 , preferably from 3 to 6%, at a temperature of between 400 and 650 ° C, preferably between 500 and 550 ° C. This operation can be performed ex situ or in situ .
  • the mesoporous silica-alumina can undergo these treatments about twenty times before it becomes necessary to renew it.
  • the invention is described in its embodiment in a step with recycling at the inlet of the first reactor in a nonlimiting manner according to the figure 1 .
  • the charge consisting of saturated compounds, resins and aromatic molecules (mono-, di-, triaromatic and PNA) arriving via a line (1) and a hydrogen flow brought by a line (2) are mixed and introduced into the hydrocracking reactor (4) by a line (3).
  • the output charge of the hydrocracker is conducted via a line (5) to a high pressure distiller (6) whose function is to separate the gaseous and liquid products.
  • the gas corresponds to unreacted hydrogen and is re-injected into the hydrocracking reactor via lines (8) and (3).
  • the liquid products are conveyed via the line (7) to a fractionation zone (9) where, thanks to the differences in boiling point, the cracked products (lighter compounds) are separated, which are thus recovered at the top of the column by line (10), of those which have not been transformed (residues 380+). These are the bottom of the column and come out through the line (11). Part of this fraction is optionally removed via line (12). The other part is sent into the recycling loop by the line (13). Then, according to the fixed PNA concentration criticality parameters, some or all of the charge is sent to an adsorption zone (17) or (18) via lines (14) and (15) or (16). .
  • an effluent whose concentration of PNA is low or zero is recovered by the lines (19) or (20) and (21). It is then sent in the line (22), which is the one carrying the part of the untreated charge by adsorption. The mixture of these two fractions is transported by the line (23) to the line containing the fresh charge, that is to say the line (1).
  • the adsorbent SA1 is obtained in the following manner.
  • the silica-alumina gels are prepared by mixing sodium silicate and water, by sending this mixture to an ion exchange resin. A solution of aluminum chloride hexahydrate in decationized silica sol water is added. In order to obtain a gel, ammonia is added, the precipitate is then filtered and the mixture is washed with a concentrated solution of water and ammonia until the conductivity of the washing water is constant. The gel resulting from this step is mixed with Pural boehmite powder so that the final composition of the mixed support in anhydrous product is, at this stage of the synthesis, equal to 70% Al 2 O 3 -30% SiO 2 . This suspension is passed through a colloid mill in the presence of nitric acid.
  • the added nitric acid content is adjusted so that the output percentage of the nitric acid mill is 8% based on the solid mixed oxide mass.
  • This mixture is then filtered in order to reduce the amount of water in the mixed cake.
  • the cake is kneaded in the presence of 10% nitric acid and then extruded.
  • the kneading is done on a Z-arm kneader.
  • the extrusion is carried out by passing the dough through a die provided with orifices 1.4 mm in diameter.
  • the extrudates thus obtained are dried at 150 ° C. and then calcined at 550 ° C.
  • MAS NMR spectra of the 27 Al solid of the catalysts show two distinct peak mass.
  • a first type of aluminum whose maximum resonates around 10 ppm ranges between -100 and 20 ppm. The position of the maximum suggests that these species are essentially of type Al VI (octahedral).
  • a second type of minority aluminum whose maximum resonates around 60 ppm ranges between 20 and 100 ppm. This founded can be broken down into at least two species. The predominant species of this massif corresponds to Al IV (tetrahedral) atoms. The proportion of octahedral Al VI is 70%.
  • the adsorbent contains two aluminosilicate zones, said zones having Si / Al ratios lower or higher than the overall Si / Al ratio determined by X-ray fluorescence.
  • One of the zones has a Si / Al ratio determined by MET of 0, 35.
  • the feed used corresponds to the residues of the bottom of a fractionation column. Its pour point is of the order of 36 ° C and its density at 15 ° C of 0.8357. It contains 95% by weight of saturated compounds (83.6% by weight of paraffinic compounds and 11.4% by weight of naphthenic compounds), 0.5% by weight of resins and 2.9% by weight of aromatic compounds, of which 2.6% by weight monoaromatic compounds, 0.56% by weight of diaromatic compounds, 0.57% by weight of triaromatic compounds, 2704 ppm of pyrene (4 rings), 1215 ppm of perylene (5 rings) and 59 ppm of coronene (7 rings).
  • the porous solids tested correspond to a mesoporous solid of the MCM-41 purely silicic type, a SiO 2 bridged beidellite type clay, a silica gel, an activated alumina, a physically activated carbon derived from a cellulosic precursor and a silica-alumina. according to the invention. They were chosen for their large specific surface and their large diameter pores between 20 and 60 ⁇ as appropriate (Table 1) combined with their regenerability by burning. Table 1: BET surface and average pore diameters of different solids.
  • the filler is contacted with different fixed bed adsorbents with a VVH of 30 at a temperature of 150 ° C and a pressure of 10 bar.
  • the adsorption selectivities of coronene relative to perylene and pyrene are calculated.
  • ⁇ i / j / VS i q ads , i / VS j q ads , j .
  • the volume of charge per volume of adsorbent that is maximally treatable is also determined so that the coronene concentration in the output charge does not exceed 2/3 of that at the inlet. This report makes it possible to estimate the adsorption capacity of solids. All of these results are shown in Table 2. Table 2: Selectivities and volume of treatable load per volume of adsorbent for different solids.
  • Regeneration of the adsorbent is carried out by burning with a flow of N 2 containing 5% O 2 at 550 ° C. As a result of these operations, 97% of the capacities of the starting solid are recovered.
  • This operation can be performed about ten times before losing 30% of capacity.

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  • 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)
  • Solid-Sorbent Or Filter-Aiding Compositions (AREA)
  • Treatment Of Liquids With Adsorbents In General (AREA)
  • Catalysts (AREA)
  • Organic Low-Molecular-Weight Compounds And Preparation Thereof (AREA)
EP06290332A 2005-03-09 2006-02-28 Procédé d'hydrocraquage avec recyclage comprenant l'adsorption de composés polyaromatiques de la fraction recyclée sur un adsorbant à base de silice-alumine à teneur limitée en macropores Expired - Fee Related EP1700899B1 (fr)

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FR0502369A FR2883005B1 (fr) 2005-03-09 2005-03-09 Procede d'hydrocraquage avec recyclage comprenant l'adsorption de composes polyaromatiques de la fraction recyclee sur adsorbant a base de silice-alumine a teneur limitee en macropores

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Cited By (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104629800A (zh) * 2013-11-13 2015-05-20 中国石油天然气股份有限公司 一种生产低硫柴油的组合工艺方法

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US9315733B2 (en) * 2006-10-20 2016-04-19 Saudi Arabian Oil Company Asphalt production from solvent deasphalting bottoms
US7763163B2 (en) * 2006-10-20 2010-07-27 Saudi Arabian Oil Company Process for removal of nitrogen and poly-nuclear aromatics from hydrocracker feedstocks
US8062509B2 (en) * 2008-09-30 2011-11-22 Uop Llc Process, system and facility for desorbing
EP2737027B1 (en) 2011-07-29 2018-12-26 Saudi Arabian Oil Company Hydrocracking process with interstage steam stripping
CN103059968B (zh) * 2011-10-21 2014-10-22 中国石油化工股份有限公司 一种加氢裂化装置的硫化开工方法
US8877040B2 (en) 2012-08-20 2014-11-04 Uop Llc Hydrotreating process and apparatus relating thereto
CN104549492B (zh) * 2013-10-23 2017-05-17 中国石油化工股份有限公司 一种废加氢裂化催化剂全回收再利用方法
FR3030564B1 (fr) 2014-12-22 2018-08-10 Axens Procede et dispositif pour la reduction des composes aromatiques polycycliques lourds dans les unites d'hydrocraquage
FR3053355B1 (fr) 2016-06-30 2019-07-26 IFP Energies Nouvelles Procede d'oligomerisation utilisant un catalyseur zeolithique et un catalyseur comprenant une silice alumine
US10011786B1 (en) * 2017-02-28 2018-07-03 Uop Llc Hydrocracking process and apparatus with HPNA removal
US10934498B1 (en) 2019-10-09 2021-03-02 Saudi Arabian Oil Company Combustion of spent adsorbents containing HPNA compounds in a membrane wall partial oxidation gasification reactor

Family Cites Families (24)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US3204006A (en) * 1962-05-14 1965-08-31 Universal Oil Prod Co Hydrotreatment of hydrocarbon stocks and separation of aromatic components
US3340316A (en) 1964-06-19 1967-09-05 Universal Oil Prod Co Separation of aromatic hydrocarbons using an improved activated carbon sorbent
US3619407A (en) 1969-12-17 1971-11-09 Union Oil Co Hydrocracking process with benzcoronenes bleedstream
US4411768A (en) 1979-12-21 1983-10-25 The Lummus Company Hydrogenation of high boiling hydrocarbons
US4447315A (en) * 1983-04-22 1984-05-08 Uop Inc. Hydrocracking process
US4618412A (en) 1985-07-31 1986-10-21 Exxon Research And Engineering Co. Hydrocracking process
US4732665A (en) 1985-12-27 1988-03-22 Uop Inc. High severity catalytic reforming process
GB8700240D0 (en) 1987-01-07 1987-02-11 Exxon Chemical Patents Inc Polynuclear aromatics
US4775460A (en) 1987-12-24 1988-10-04 Uop, Inc. Hydrocracking process with feed pretreatment
US4961839A (en) 1988-05-23 1990-10-09 Uop High conversion hydrocracking process
US5124023A (en) 1988-11-28 1992-06-23 Union Oil Company Of California Continuous removal of polynuclear aromatics from hydrocarbon recycle oil
US4954242A (en) 1989-07-19 1990-09-04 Uop Process for refractory compound removal in a hydrocracker recycle liquid
US5007998A (en) 1990-03-26 1991-04-16 Uop Process for refractory compound conversion in a hydrocracker recycle liquid
US5232577A (en) 1990-08-14 1993-08-03 Chevron Research And Technology Company Hydrocracking process with polycyclic aromatic dimer removal
US5139646A (en) 1990-11-30 1992-08-18 Uop Process for refractory compound removal in a hydrocracker recycle liquid
US5120426A (en) 1990-12-21 1992-06-09 Atlantic Richfield Company Hydrocracking process
US5139644A (en) 1991-04-25 1992-08-18 Uop Process for refractory compound conversion in a hydrocracker recycle liquid
US5190633A (en) * 1992-03-19 1993-03-02 Chevron Research And Technology Company Hydrocracking process with polynuclear aromatic dimer foulant adsorption
US5464526A (en) 1994-05-27 1995-11-07 Uop Hydrocracking process in which the buildup of polynuclear aromatics is controlled
US5792898A (en) 1996-09-27 1998-08-11 Uop Llc Process for the management of mononuclear and polynuclear aromatic compounds produced in a hydrocarbon dehydrogenation reaction zone
US6217746B1 (en) 1999-08-16 2001-04-17 Uop Llc Two stage hydrocracking process
EP1370628A1 (en) 2001-03-20 2003-12-17 Uop Llc Two stage hydrocracking process
FR2846574B1 (fr) 2002-10-30 2006-05-26 Inst Francais Du Petrole Catalyseur et procede d'hydrocraquage de charges hydrocarbonees
CA2590108C (fr) * 2004-12-23 2012-12-04 Institut Francais Du Petrole Catalyseur zeolithique a teneur controlee en element dopant et procede ameliore de traitement de charges hydrocarbonees

Cited By (2)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
CN104629800A (zh) * 2013-11-13 2015-05-20 中国石油天然气股份有限公司 一种生产低硫柴油的组合工艺方法
CN104629800B (zh) * 2013-11-13 2016-06-08 中国石油天然气股份有限公司 一种生产低硫柴油的组合工艺方法

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ES2308691T3 (es) 2008-12-01
US7588678B2 (en) 2009-09-15
US20060213808A1 (en) 2006-09-28
FR2883005B1 (fr) 2007-04-20
EP1700899A1 (fr) 2006-09-13
DE602006001664D1 (de) 2008-08-21
CA2538186C (fr) 2013-06-25
JP4875908B2 (ja) 2012-02-15
FR2883005A1 (fr) 2006-09-15
CA2538186A1 (fr) 2006-09-09

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