Classifications

• • 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
  • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
  • C10G47/22—Non-catalytic cracking in the presence 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
  • 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
• • 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
  • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
• • 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
  • C10G65/10—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including only cracking steps
• • 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
  • C10G7/00—Distillation of hydrocarbon oils
• • 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
  • C10G7/00—Distillation of hydrocarbon oils
  • C10G7/006—Distillation of hydrocarbon oils of waste oils other than lubricating oils, e.g. PCB's containing oils
• • 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
  • C10G2300/10—Feedstock materials
  • C10G2300/1096—Aromatics or polyaromatics
• • 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

Definitions

• the invention relates to a method and a device for reducing the concentration of heavy polycyclic aromatic compounds (HPNA) in the recycling loop of the hydrocracking units.
• HPNA heavy polycyclic aromatic compounds
• Hydrocracking processes are commonly used in refineries to convert hydrocarbon mixtures into easily recoverable products. These methods can be used to transform light cuts such as, for example, lighter-weighted species (LPG). However, they are usually used instead to convert heavier loads (such as heavy petroleum or synthetic cuts, for example vacuum distillation gas oils or effluents from a Fischer-Tropsch unit) into gasoline or naphtha, kerosene, diesel fuel. . This type of process is also used to produce oils.
• LPG lighter-weighted species
• part of the unconverted feed is recycled either to the reaction section in which it has already passed or to an independent reaction section.
• This induces an undesirable accumulation of the polycyclic aromatic compounds, formed in the reaction section during the cracking reactions, in the recycling loop.
• These compounds poison the hydrocracking catalyst, which reduces the catalytic activity as well as the cycle time. They can also precipitate or settle in the cold parts of the unit, thus generating malfunctions.
• HPNA compounds are defined as polycyclic or polynuclear aromatic compounds which thus comprise several fused rings or benzene rings. They are usually called HPA, Heavy Polynuclear Aromatics according to the English terminology, PNA or HPNA. Typically, the so-called heavy HPNAs comprise at least 4 or even at least 6 benzene rings in each molecule. Compounds with less than 6 cycles (pyrene derivatives for example) can be more easily hydrogenated and are therefore less likely to poison catalysts.
• US Patent 4,961,839 discloses a hydrocracking process for increasing pass conversion by using high hydrogen flow rates in the reaction zone, vaporizing a large proportion of the hydrocarbons fed to the product separation column, and concentrating the polycyclic aromatic compounds in a small heavy fraction which is extracted from this column.
• a heavy fraction is withdrawn at a plateau above the feed point and below the diesel distillate withdrawal point; this heavy fraction is recycled to hydrocracking.
• the bottom of the column (residue) is recycled directly into the fractionation column.
• This type of technique certainly allows a reduction in the concentration of HPNA in the recycling loop to the reactor, but leads to significant yield losses and significant costs related to the amounts of hydrogen.
• Patent applications and WO 2012/052042 and WO 2012/0521 1 6 (corresponding to US-2013/0220885) describe a hydrocracking process in which the bottom of the Fractionation column (residue) is stripped countercurrently in a stripping column.
• the light fraction obtained after stripping is returned to the fractionation column and the heavy fraction resulting from the stripping is at least partially purged, the other part of this fraction can be recycled to the stripping column.
• the method of the invention allows not only to concentrate the polycyclic aromatic hydrocarbons in unconverted fractions (residues) in order to eliminate them and reduce the amount of residue purged to increase the conversion, but also to improve the yield of valuable products. (For example avoiding over-cracking of diesel) and / or the catalytic cycle time compared to previous methods.
• the invention also has the advantage of considerably reducing the amount present in hydrocracking of HPNA having at least 6 aromatic rings, which are the most refractory to the reactions involved during hydrocracking.
• the process according to the invention is based on the setting up of a lateral withdrawal below the feed point of the column.
• the separation of the liquid is preferably carried out by combining a stripper with the fractionation column, which strips said stripper. fraction withdrawn.
• the invention relates to a process for hydrocracking a petroleum feedstock comprising at least 10% by volume of compounds boiling above 340 ° C., comprising a hydrocracking step, optionally followed by a separation of the feed gases.
• a fractionation step of said effluent which separates at least one distillate and a residue, said residue being partly recycled to the hydrocracking step and another part of the residue being purged, said step of fractionation comprises a distillation in a column provided with trays, column in which
• said at least partially vaporized effluent feeds the column onto at least one feed tray, said distillate is drawn off at a draw-off plate,
• a stripping gas is injected at an injection point situated below the feed tray, a process in which
• a part of the flow present at the level of the feed tray is withdrawn from the column.
• a part of the flow present at a plateau located below the supply tray and close to said feed tray is withdrawn from the column, and preferably at the level of the plateau closest to the plateau. power.
• said withdrawn stream can be recycled to the hydrocracking step directly (i.e. without treatment) or after separation of the gases (for example by adsorption, stripping ...) or after further separation (distillation ).
• said withdrawn stream is recycled directly to the hydrocracking stage.
• all or part, and preferably all, of said stream withdrawn from said tray (II) is stripped in an external stripping step by a stripping gas, and all or part, and preferably the totality of the separated gaseous effluent is recycled to the column above the plate from which said flow has been withdrawn, and all or part, and preferably all, of the separated liquid effluent is recycled in step d hydrocracking.
• the separated gaseous effluent is recycled to the column at the level of the plateau closest to the plateau from which said flow has been withdrawn. It will be noted that, according to the invention and preferably, there is no recycling of the liquid fraction, separated at the stripping step, to the fractionation column.
• the stream withdrawn at the plateau (I) or plateau (II) has an HPNA concentration of less than 500 ppm by weight, preferably less than 350 ppm by weight and very preferably less than 200 ppm by weight. It most often has a proportion of at least 70% by weight of unconverted hydrocarbons, preferably of at least 80% by weight of unconverted hydrocarbons and very preferably of at least 90% by weight of unconverted hydrocarbons.
• the process operates in the presence of a stripping gas injected into the fractionation step.
• a stripping gas injected into the fractionation step.
• it is water vapor, preferably at a pressure of between 0.2 and 1.5 MPa.
• the stripping gas injected into the external stripping step is preferably water vapor, preferably at a pressure of between 0.2 and 1.5 MPa.
• the hydrocracking step conventionally takes place at a temperature above 200 ° C., a pressure greater than 1 MPa, a space velocity of 0.1 to 20 h -1 , and the H 2 / hydrocarbons volume ratio is 80 to 5000 Nl / I.
• the invention also relates to an installation which is advantageously used to carry out the method according to the invention.
• a hydrocracking section (2) provided with a line (1) for entering the charge and a line (8) for introducing hydrogen
• a fractionation section (12) comprising at least one distillation column provided with trays, said column comprising: - at least one line (1 1) input of the hydrocracked effluent at least partially vaporized on at least a feeding tray,
• the apparatus further comprising:
• the installation comprises at least one line (18) for recycling all of said stream withdrawn directly into the hydrocracking stage.
• the line (18) comprises a gas separation unit located before the hydrocracking section. This unit may for example be an adsorber or a stripper or a distillation column.
• the installation further comprises:
• a stripper (25) external to the column provided with an inlet line (21) for withdrawing said stream, a line (26) for injecting the stripping gas, and an outlet line (22). of the gaseous fraction, of a line (23) for the exit of the liquid fraction,
• a line (22) for recycling all or part, and preferably all, of said gaseous fraction in said column the line (22) opening into the column above the plate from which said flow has been withdrawn, and preferably at the level of the plateau closest to the plateau from which said stream has been withdrawn,
• the installation does not include a recycling line of the residue in the column.
• the residue is preferably completely purged.
• the charges are defined by their boiling point T5 (as explained below).
• the conversion of the charge is defined with respect to the cut point of the residue.
• the unconverted fraction is called residue.
• the converted fraction comprises the desired fractions (objectives) by the refiner.
• the purged part refers to a part that leaves the process.
• Figure 1 shows the prior art.
• the configurations 2c and 2d of FIG. 2 represent the invention.
• Figures 2c and 2d are understood in combination with Figure 1, and more specifically with the essential elements of Figure 1 cited in the claims.
• FIG. 1 shows a hydrocracking process scheme according to the prior art.
• the feed (line 1) composed of hydrocarbons of petroleum origin and / or synthetic hydrocarbons of mineral or biological source is mixed with hydrogen supplied by lines (5) (recycle) and / or (6) ( make-up hydrogen) via the compressor (7) and the line (8).
• the charge / hydrogen mixture thus produced is sent to the hydrocracking section (2).
• This section includes one or more reactors in fixed bed or bubbling bed.
• each reactor may comprise one or more catalyst beds hydrocracking hydrocarbons of the lighter hydrocarbon feedstock.
• the hydrocracking section comprises one or more bubbling bed reactors
• a stream comprising liquid from the solid and gas flows vertically through a reactor containing a catalyst bed.
• the catalyst in the bed is kept in random motion in the liquid.
• the gross volume of the catalyst dispersed through the liquid is therefore greater than the volume of the catalyst at standstill.
• This technology is widely described in the literature.
• a mixture of hydrocarbon liquid and hydrogen is passed through the bed of catalyst particles at such a rate that the particles are put into operation. random movement and thus suspended in the liquid.
• the expansion of the catalyst bed in the liquid phase is controlled by the flow of recycle liquid so that in the equilibrium state, most of the catalyst does not exceed a defined level in the reactor.
• the catalysts are in the form of extrudates or balls, preferably of diameter between 0.8 mm and 6.5 mm in diameter.
• the reactors used in a bubbling bed process are generally designed with a central vertical recirculation conduit which serves as a flow tube for liquid recycle from the catalyst free zone above the bubbling bed catalyst via a pump. recycle that recycle the liquid in the catalytic zone.
• the liquid recycle allows both to maintain uniformity of temperature in the reactor and to maintain the catalyst bed in suspension.
• the hydrocracking section may be preceded or include one or more beds of hydrotreatment catalyst (s).
• the effluent of the hydrocracking section (2) is sent via line (3) to a separation zone (4) making it possible to recover firstly a gaseous fraction (5) and a liquid fraction (9).
• the gaseous fraction (5) contains excess hydrogen which has not reacted in the reaction section (2). It is generally combined with fresh hydrogen arriving via the line (6) to be recycled as indicated above.
• the liquid fraction (9) is heated by any means (10), for example an oven optionally associated with an exchanger (not shown), in order to be at least partially vaporized, before feeding the fractionation section (12) via the line (1 1).
• the fractionation section (12) comprises one or more distillation columns equipped with trays and internals making it possible to separate different (distillate) sections which are recovered by means of lines (13) and (14), plus possibly other side rackings. These sections have ranges of boiling points located for example in the range of gasoline, kerosene and gas oil.
• An injection of stripping gas may be provided via the line (19). This line is located between the hydrocracked effluent feed tray (line 1 1) and the residue discharge point (line 15a).
• Part of the residue can be purged via line (1 6), another part recycled to the hydrocracking section through lines (2) and (1 8) and another part recycled to the fractionation section (line 15b) .
• a part (line 15b) of the residue of the line (15a) is mixed with the feed (line 9) upstream of the furnace (10) of the fractionation section and recycled as a mixture (line 1 1) with this cut to the splitting section.
• the purge (1 6) allows in particular to eliminate at least in part the HPNA compounds which without this purge could accumulate in the recycling loop.
• the zone E traced in FIG. 1 delimits the modified part within the scope of the present invention.
• FIGS 2c and 2d show the invention.
• the line (15b) (recycling of the residue to the fractionation column) is deleted in the invention. It is the same for recycling the residue to hydrocracking.
• the fractionation section (12) comprises a single fractionation column. However, the invention could be carried out with several fractionating columns and at least one column would then comprise a zone E according to the invention. According to Figure 2c, the liquid fraction (1 1) which was previously at least partially vaporized feeds the fractionation section (12).
• a stripping gas is injected into the column (line 19).
• the injection point is located below the feed tray and above the residue discharge point. It is preferably close to the point of evacuation of the residue at the bottom of the column.
• FIG. 2c differs from FIG. 1 in particular in that a lateral withdrawal (line 20) is added at one of the plates of the column.
• a lateral withdrawal line 20
• One or more rackings can be set up at the level of the column. It is thus withdrawn part of the flow present at the level of at least one plate (I).
• This tray may be the feed tray, in a preferred mode.
• the tray (I) shown is the feed tray.
• This withdrawal (line 20) is preferably at a plateau near the feed tray, and preferably at the plateau closest to the feed tray.
• the lateral withdrawal (line 20) is positioned in such a way that the withdrawn stream has a low HPNA concentration of less than 500 ppm by weight, preferably less than 350 ppm by weight and very preferably less than 200 ppm by weight, and most often a significant proportion of hydrocarbons not converted in the hydrocracking section by at least 70% by weight of unconverted hydrocarbon, preferably at least 80% by weight of nonhydrocarbons converted and very preferably at least 90% by weight of unconverted hydrocarbons.
• racking (line 20) is preferably positioned at the level of the feed tray or below the feed tray, and in the latter case, preferably at the plateau closest to the tray. power.
• All or part of said withdrawn stream is recycled to the hydrocracking step. It can be recycled directly (i.e. without treatment) or after any gas separation. Preferably, it is recycled directly into the hydrocracking step. According to the invention, the residue is not recycled in the column or in the hydrocracking step. It is completely purged. Note also that the stream withdrawn from the tray (I) is not recycled in the column (12).
• FIG. 2d represents a preferred embodiment of the invention with the addition of a second lateral withdrawal at a plateau (II) different from the plateau (I).
• a part of the flow present at the level of at least one plate (II) situated between the feed tray and the extraction tray of the heaviest distillate fraction is withdrawn (line 21) from the column. .
• One or more rackings can be set up at the level of the column.
• This withdrawal (line 21) is preferably close to the feed tray.
• a portion of the flow present at the upper tray closest to the feed tray is withdrawn from the column.
• the lateral withdrawal (line 21) is positioned in such a way that the withdrawn stream has a low HPNA concentration of less than 500 ppm by weight, preferably less than 350 ppm by weight and very preferably less than 200 ppm by weight, and most often a significant proportion of unconverted hydrocarbons in the hydrocracking section of at least 70 wt% hydrocarbon unconverted, preferably at least 80% by weight unconverted hydrocarbons and very preferably at least 90% by weight unconverted hydrocarbons.
• the racking (line 21) is preferably positioned at the level of the feed tray or above the feed tray, and in the latter case, preferably at the plateau closest to the tray. power.
• All or part of said withdrawn stream is recycled to the column after separation of the liquid.
• the stream withdrawn (line 21) is stripped in an external stripping step (stripper 25) by a stripping gas (brought by the line 26).
• All or part of the separated gaseous effluent is recycled (line 22) in the column; according to Figure 2d, the entire gaseous effluent is recycled.
• the gaseous effluent is recycled to the column above which the flow has been withdrawn.
• better performances are obtained when the gaseous effluent is recycled to the column at the level of the plateau closest to the plateau from which the flow has been withdrawn.
• liquid effluent (line 23) is recycled in the hydrocracking step. It can be recycled directly (i.e. without treatment) or after any gas separation. Preferably, it is recycled directly into the hydrocracking step.
• all the liquid effluent (line 23) is mixed with the stream (line 20) of the lateral withdrawal of the plate (I) and the mixture is recycled (line 18) to the hydrocracking stage.
• Said lateral stripper (25) operates with the injection of a stripping gas (line 26).
• This gas is preferably steam, preferably low-pressure steam, preferably at a pressure of between 0.2 and 1.5 MPa.
• the embodiment of FIG. 2d leads to better performances than the embodiment of FIG. 2c.
• fillers can be processed by the hydrocracking processes. Generally they contain at least 10% volume, usually at least 20% volume, and often at least 80% 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.
• RAT atmospheric residues
• RSV vacuum residues
• deasphalted oils or the charge can be a deasphalted oil, effluents d a Fisher-Tropsch unit or any mixture of the aforementioned fillers.
• RAT atmospheric residues
• RSV vacuum residues
• deasphalted oils or the charge can be a deasphalted oil, effluents d a Fisher-Tropsch unit or any mixture of the aforementioned fillers.
• the feeds have a T5 boiling point above 150 ° C (i.e. 95 percent of the compounds present in the feed have a boiling point above 150 ° C).
• the T5 point is generally about 150 ° C.
• the T5 is generally greater than 340 ° C., or even greater than 370 ° C.
• the usable fillers are therefore in a wide range of boiling points. This range generally extends from diesel to VGO, passing through all possible mixtures with other loads, for example the LCO.
• the nitrogen content of the feedstocks treated in the hydrocracking processes is usually greater than 500 ppm by weight, generally between 500 and 10,000 ppm by weight, more generally between 700 and 4500 ppm by weight and even more generally between 800 and 800 ppm by weight. and 4500 ppm weight.
• the sulfur content of the feedstocks treated in the hydrocracking processes is usually between 0.01 and 5% by weight, generally between 0.2 and 4% by weight and even more generally between 0.5 and 3%. weight.
• the charge may optionally contain metals.
• the cumulative nickel and vanadium content of the feeds treated in the hydrocracking processes is preferably less than 10 ppm by weight, preferably less than 5 ppm by weight and even more preferably less than 2 ppm by weight.
• the asphaltenes content is generally less than 3000 ppm by weight, preferably less than 1000 ppm by weight, more preferably less than 300 ppm by weight.
• the feedstock contains resins and / or asphaltenes-type compounds
• the catalysts or guard beds used are in the form of spheres or extrudates. Any other form can be used. Among the particular forms possible without this list being exhaustive: hollow cylinders, hollow rings, Raschig rings, serrated hollow cylinders, crenellated hollow cylinders, so-called 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.
• These catalysts may have macroporosity.
• 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 between 0.1 and 6h “1 , more preferably between 0.2 and 3h " 1 , and the amount of hydrogen introduced is such that the volume ratio liter of hydrogen / liter of hydrocarbon is between 80 and 5000 Nl / I and most often between 100 and 3000 Nl / I.
• the invention can be used for all hydrocrackers, namely:
• maxi-naphtha hydrocracker with a cutting point residue generally between 150 ° C and 190 ° C, preferably between 1 60 ° C and 190 ° C, and most often 170 ° C-180 ° C - maxi-kerosene hydrocracker with a cutting point residue generally between 240 ° C and 290 ° C, and most often 260 ° C-280 ° C
• maxi diesel hydrocracker with a cutting point residue generally between 340 ° C and 385 ° C, and most often 360 ° C-380 ° C.
• the hydrocracking / hydroconversion processes using the catalysts according to the invention cover the pressure and conversion ranges from mild hydrocracking to high pressure hydrocracking.
• mild hydrocracking is meant hydrocracking leading to moderate conversions, generally less than 40 percent, and operating at low pressure, generally between 2 MPa and 9 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.
• Hydrocracking can be operated at high pressure (at least 10 MPa).
• the hydrocracking can be carried out according to a so-called two-step hydrocracking scheme with intermediate separation between the two reaction zones, in a given step, the hydrocracking catalyst can be used in one or in both reactors in association or not with a hydrorefining catalyst located upstream of the hydrocracking catalyst.
• the hydrocracking can be operated according to a second variant, called in one step.
• This variant generally comprises in the first place a deep hydrorefining which aims to carry out extensive hydrodenitrogenation and hydrodesulfurization of the feed before it is sent to the hydrocracking catalyst itself, in particular in the case where this it comprises a zeolite.
• This extensive hydrorefining of the feed results in a limited conversion of this feed into lighter fractions. The conversion, which remains insufficient, must therefore be completed on the more active hydrocracking catalyst.
• the hydrocracking section may contain one or more identical or different catalyst beds.
• amorphous basic solids for example alumina or silicas, are used.
• aluminas or basic zeolites optionally added with at least one Group VIII hydrogenating metal and preferably also containing at least one Group VIB metal.
• These basic zeolites are composed of silica, alumina, and one or more exchangeable cations such as sodium, magnesium, calcium or rare earths.
• the catalyst is generally composed of a crystallized zeolite on which small amounts of a Group VIII metal are deposited, and also more preferably of a Group VIB metal.
• the zeolites that can be used are natural or synthetic and may be chosen, for example, from X, Y or L zeolites, faujasite, mordenite, erionite or chabasite.
• the hydrocracking can be carried out in one or more bubbling-bed reactors, with or without liquid recycling of the unconverted fraction, optionally in combination with a hydrorefining catalyst located in a fixed-bed or bubbling-bed reactor upstream of the reactor. hydrocracking catalyst.
• the bubbling bed operates with removal of spent catalyst and daily addition of new catalyst to maintain stable catalyst activity.
• Liquid / gas separation (4) separates the liquid and the gas present in the effluent leaving the hydrocracking unit. Any type of separator allowing this separation can be used, for example a flash ball, a stripper, or even a simple distillation column.
• the fractionation section is generally composed of one or more columns comprising a plurality of trays and / or internal packings which can preferably be operated countercurrently. These columns are usually stripped steamed and include a reboiler to facilitate vaporization. It makes it possible to separate the hydrogen sulphide (H2S) and the light components (methane, ethane, propane, butane, etc.) from the effluents, as well as the hydrocarbon cuts having boiling points in the field of gasolines, kerosene, a gasoil and a heavy fraction recovered at the bottom of the column, all or part of which can be recycled to the hydrocracking section.
• H2S hydrogen sulphide
• the light components methane, ethane, propane, butane, etc.
• the splitting of the stream 1 1 in the column 12 was simulated by programming via the software PRO / II version 8.3.3, marketed by the SimSci company.
• the physical and analytical properties of the resulting fluxes were simulated and compared with the physical and analytical properties of the actual samples.
• the simulation PRO / II could establish the properties of the output stream of the fractionation column, in particular the distribution in HPNA was able to to be modeled.
• Relative density SG p hantiiion EC at 20 ° C / w H20 at 4 ° C where p is the density in g / cm 3
• Example 2 Configuration 2c Table 3 below gives the characteristics of the currents 1 1, 1 6 and 1 8 (identical to 20) in the configuration 2c resulting from the simulation PRO / I I. The operating conditions of the column used for the simulation are reported in Table 4: Table 3: Flux Properties According to the Schema of Figure 2c
• Relative density SG p hantiiion EC at 20 ° C / p H 2o at 4 ° C or p is the density in g / cm 3
• the configuration 2c makes it possible to maximize the amount of HPNA (3962 ppm by weight compared with 902 ppm by weight of the configuration 1) in the unconverted fraction which is purged via the line 1 6. At the same time, the amount of HPNA is minimized in the stream that goes back to the reaction section via line 18 (707 ppm weight compared with 902 ppm weight of configuration 1) which reduces the amount of HPNA by 21.6%.
• the proportion of heavy refractory and poisonous HPNA (Naphto [8.2.1 abc] + coronene + Ovalene) relative to the amount of total HPNA in the flow that leaves to the reaction section is lower for configuration 2c (27.8%) than for configuration 1 (36.3%). This indicates that not only is there less total HPNA in the stream that returns to the reaction section via line 1 8 but in addition to the proportion of heavy refractory and poisoning HPNA (Naphto [8.2,1 ab] coronene + Ovalene) is weaker.
• Table 5 gives the characteristics of currents 1 1, 1 6 and 1 8 in the 2d configuration resulting from simulation PRO / I I.
• the operating conditions of the column used for the simulation are reported in Table 6:
• Relative density SG p hantiiion EC at 20 ° C / p H 2o at 4 ° C or p is the density in g / cm 3
• Table 6 Operative conditions of the column
• the configuration 2d makes it possible to maximize the amount of HPNA (4959 ppm by weight to be compared with 902 ppm by weight of configuration 1) in the unconverted fraction which is purged via the line (1 6 ).
• the amount of HPNA is minimized in the stream flowing back to the reaction section via line (18) (644 ppm by weight to be compared with 902 ppm by weight of configuration 1) which reduces the amount of HPNA by 28.6. %.
• the proportion of heavy refractory and poisonous HPNA (Naphto [8.2,1 abc] coronene + Ovalene) relative to the amount of total HPNA in the flow (18) that returns to the reaction section is higher. weak for configuration 2d (20.7%) than for configuration 1 (36.3%). This indicates that not only is there less total HPNA in the flow that returns to the reaction section via line (18) but in addition that the proportion of heavy refractory and poisoning HPNA (Naphto [8.2.1 abc] coronene + Ovalene) is weaker.
• this configuration also makes it possible to minimize the amount of diesel that is returned to the reaction section via line 18 since the amount of diesel returned to the reaction section is only 6.8% by weight compared with 10.9% by weight. in configuration 1.

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