EP3237578B1 - Process and apparatus for the reduction of heavy polycyclic aromatic compounds in hydrocracking units - Google Patents

Description

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.

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.

In order to increase the conversion of the hydrocracking units, 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.

There is therefore a need to improve the hydrocracking process in order to reduce the formation of polycyclic aromatic compounds, or to eliminate them without reducing the yield of recoverable products.

The 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. As a result, we were particularly interested in the most representative compounds of families with 6 or more aromatic rings, such as Coronene (24-carbon compound), dibenzo (e, ghi) perylene (26 carbons), naphtho [8 , 2.1, abc] coronene (30 carbons) and ovalene (32 carbons), which are the most easily identifiable and quantifiable compounds for example by chromatography.

The patent US 7,588,678 of the applicant describes a hydrocracking process with recycling of the unconverted fraction 380 ° C +, in which process the HPNA compounds are removed from the recycled fraction by means of an adsorbent. Other techniques for reducing the amount or elimination of the HPNAs are described in the prior art of this patent, such as, for example, their reduction via hydrogenation or their precipitation followed by filtration.

The patent US 4,961,839 discloses a hydrocracking process for increasing pass conversion 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 the reaction zone. a small heavy fraction that is extracted from this column. In this process, a heavy fraction is drawn off 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 2012/052116 (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.

These processes have led to improvements in the reduction of HPNA but often to the detriment of yields and costs.

Licences US 2,958,652 , US 4,162,963 , US 4,040,944 , US 2,853,433 , US 3,166,489 , US 3,891,539 , WO 03/004586 and EP 0 143 862 describe a hydrocracking process.

The method of the invention allows not only to concentrate the polycyclic aromatic hydrocarbons in unconverted fractions (residues) in order to eliminate them and to reduce the amount of residue purged to increase the conversion, but also to improve the yield of recoverable 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 introduction of a lateral withdrawal below the feed point of the column. The separation of the liquid preferably takes place by associating a stripper with the fractionation column, which strippes said fraction withdrawn.

• ledit effluent au moins partiellement vaporisé alimente la colonne sur au moins un plateau d'alimentation,
• ledit distillat est soutiré au niveau d'un plateau de soutirage,
• ledit résidu est évacué à un point d'évacuation,
• et un gaz de stripage est injecté à un point d'injection situé en-dessous du plateau d'alimentation, procédé dans lequel
• il est soutiré de la colonne une partie du flux présent au niveau d'au moins un plateau (I) qui est le plateau d'alimentation ou un plateau situé entre le plateau d'alimentation et ledit point d'injection du gaz de stripage,
• tout ou partie, et de préférence la totalité, dudit flux soutiré est recyclée dans l'étape d'hydrocraquage,
• et le résidu est entièrement purgé

dans lequel il est soutiré de la colonne une partie du flux présent au niveau d'au moins un plateau (II) situé entre le plateau d'alimentation et le plateau de soutirage de la fraction distillat la plus lourde, ledit au moins un plateau (II) étant situé au-dessus dudit plateau d'alimentation,
dans lequel tout ou partie, et de préférence la totalité, dudit flux soutiré dudit plateau (II) est strippé dans une étape de stripage externe par un gaz de stripage, et tout ou partie, et de préférence la totalité, l'effluent gazeux séparé est recyclé dans la colonne au-dessus du plateau duquel ledit flux a été soutiré, et tout ou partie, et de préférence la totalité, de l'effluent liquide séparé est recyclé dans l'étape d'hydrocraquage.More specifically, 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. the hydrocracked effluent, then a fractionation step of said effluent, which separates at least one distillate and a residue, said fractionation step comprises 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 plate,
• said residue is evacuated to an evacuation point,
• and a stripping gas is injected at an injection point located below the feed tray, a process in which
• a part of the flow present at the level of at least one plate (I) which is the feed plate or a plate situated between the feed plate and the said point of injection of the stripping gas is withdrawn from the column,
• all or part, and preferably all, of said withdrawn stream is recycled to the hydrocracking step,
• and the residue is completely purged

in which a part of the flow present at the level of at least one tray (II) situated between the feed tray and the extraction tray of the heavier distillate fraction is withdrawn from the column, said at least one tray ( II) being located above said feed tray,
wherein all or part, and preferably all, of said stream withdrawn from said plate (II) is stripped in an external stripping step by a stripping gas, and all or part, and preferably all, the separate gaseous effluent is recycled to the column above the plate from which said stream has been withdrawn, and all or part, and preferably all, of the separated liquid effluent is recycled to the hydrocracking step.

Advantageously, 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.

Advantageously, said stream withdrawn can be recycled in the hydrocracking step directly (ie without treatment) or after separation of the gases (for example by adsorption, stripping ...) or after further separation (distillation ...). Preferably, said withdrawn stream is recycled directly to the hydrocracking stage. It will be noted that, according to the invention and preferably, there is no recycling of said stream withdrawn into the column.

Preferably, 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. It will also be noted that according to the invention, all the residue is purged.

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.

Preferably, the process operates in the presence of a stripping gas injected into the fractionation step. Preferably, 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 greater than 200 ° C., a pressure greater than 1 MPa, a space velocity of 0.1 to 20 h ^-1 , and the volume ratio H 2 / hydrocarbons is 80 at 5000NI / I.

The invention also relates to an installation which is advantageously used to carry out the method according to the invention.

• une section d'hydrocraquage (2) munie d'une ligne (1) d'entrée de la charge et d'une ligne (8) d'entrée de l'hydrogène,
• éventuellement suivie d'une zone de séparation (4) de l'effluent pour séparer une fraction gazeuse,
• suivie d'une section de fractionnement (12) comprenant au moins une colonne de distillation munie de plateaux, ladite colonne comportant :
  • au moins une ligne (11) d'entrée de l'effluent hydrocraqué au moins partiellement vaporisé sur au moins un plateau d'alimentation,
  • au moins une ligne (14) pour le soutirage d'au moins un distillat au niveau d'un plateau de soutirage,
  • au moins une ligne (16) d'évacuation sous forme de purge de la totalité du résidu,
• et comprenant au moins une ligne (19) pour l'injection d'un gaz de stripage, le point d'injection étant situé en-dessous du plateau d'alimentation,

installation comprenant en outre :

• au moins une ligne (20) pour le soutirage d'une partie du flux présent au niveau d'au moins un plateau (I) qui est le plateau d'alimentation ou un plateau situé entre le plateau d'alimentation et ledit point d'injection du gaz de stripage,
• au moins une ligne (18) pour le recyclage de tout ou partie dudit flux soutiré, et de préférence la totalité, dans l'étape d'hydrocraquage,
  • au moins une ligne (21) pour le soutirage d'une partie du flux présent au niveau d'au moins un plateau (II) situé entre le plateau d'alimentation et le plateau de soutirage de la fraction distillat la plus lourde, ledit au moins un plateau (II) étant situé au-dessus dudit plateau d'alimentation,
  • un stripeur (25) externe à la colonne, muni d'une ligne (21) d'entrée dudit flux soutiré, d'une ligne (26) d'injection d'un gaz de stripage, d'une ligne (22) de sortie de la fraction gazeuse, d'une ligne (23) de sortie de la fraction liquide,
  • une ligne (22) de recyclage de tout ou partie, et de préférence de la totalité, de ladite fraction gazeuse dans ladite colonne, la ligne (22) débouchant dans la colonne au-dessus du plateau duquel ledit flux à été soutiré,
  • une ligne (23) de recyclage de tout ou partie, et de préférence de la totalité, de ladite fraction liquide dans l'étape d'hydrocraquage.

She understands :

• a hydrocracking section (2) provided with a line (1) for entering the charge and a line (8) for introducing hydrogen,
• optionally followed by a separation zone (4) of the effluent to separate a gaseous fraction,
• followed by a fractionation section (12) comprising at least one distillation column provided with trays, said column comprising:
  • at least one inlet line (11) of the hydrocracked effluent that is at least partially vaporized on at least one feed tray,
  • at least one line (14) for withdrawing at least one distillate at a draw plate,
  • at least one drain line (16) for purging the entire residue,
• and comprising at least one line (19) for injecting a stripping gas, the injection point being located below the feed tray,

installation further comprising:

• at least one line (20) for withdrawing a portion of the flow present at at least one tray (I) which is the feed tray or a tray located between the feed tray and said feed point; injection of the stripping gas,
• at least one line (18) for recycling all or part of said stream withdrawn, and preferably all, in the hydrocracking step,
  • at least one line (21) for withdrawing a portion of the flux present at at least one plate (II) located between the feed tray and the draw plate of the heaviest distillate fraction, said at least one tray (II) being located above said feed tray,
  • a stripper (25) external to the column, provided with an inlet line (21) of said withdrawn stream, a line (26) for injecting a stripping gas, a line (22) of leaving the gaseous fraction, an exit line (23) 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,
  • a line (23) for recycling all or part, and preferably all, of said liquid fraction in the hydrocracking step.

Preferably, the installation comprises at least one line (18) for recycling all of said stream withdrawn directly into the hydrocracking stage. In Another provision, 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.

of all of said liquid fraction in the hydrocracking step.

Preferably, there is no recycle line of the liquid fraction, separated at the stripping step, to the fractionation column.

The invention will be better understood from the description of the figures.

In the text, 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.

The figure 1 represents the prior art. The configuration 2c of the figure 2 represents the prior art. The configuration 2d 2d of the figure 2 represents the invention. The Figures 2c and 2d understand each other in combination with the figure 1 , and more specifically with the essential elements of the figure 1 cited in the claims.

The principle will be explained from the Figure 2c .

The figure 1 shows a hydrocracking process scheme according to the prior art. For ease of reading, the description of the implementation conditions is given later in the text.

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.

When the hydrocracking section comprises one or more fixed bed reactors, each reactor may comprise one or more catalyst beds hydrocracking hydrocarbons of the lighter hydrocarbon feedstock. When 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.

In a bubbling bed process large amounts of hydrogen gas and light hydrocarbon vapors rise through the reaction zone and then into a catalyst-free zone. The liquid from the catalytic zone is partly recycled in the bottom of the reactor after separation of a gaseous fraction and partly removed from the reactor as a product, usually in the upper part of the reactor.

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 (11). The fractionation section (12) comprises one or more distillation columns equipped with trays and internals for separating different recoverable fractions (distillates) which are withdrawn 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.

At the bottom of the column, a heavier unconverted fraction (residue) is recovered (line 15a).

An injection of stripping gas may be provided via the line (19). This line is located between the hydrocracked effluent feed tray (line 11) and the residue discharge point (line 15a).

Part of the residue can be purged via line (16), another portion recycled to the hydrocracking section through lines (2) and (18) and another portion recycled to the fractionation section (line 15b).

According to figure 1 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 11) with this cut towards the splitting section. The purge (16) allows in particular to eliminate at least partially HPNA compounds which without this purge could accumulate in the recycling loop.

Zone E traced on the figure 1 delimits the modified part in the context of the present invention.

The Figure 2c present the prior art and the figure 2d presents the invention.

We will not repeat the elements described above. It will be noted that 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 (11) which has been previously at least partially vaporized feeds the fractionation section (12).

A stripping gas is injected into the column (line 19). Advantageously, this is steam, preferably low-pressure steam, preferably at a pressure of between 0.2 and 1.5 MPa (0.1 MPa = 1 bar). 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.

The Figure 2c is different from the figure 1 notably in that a lateral withdrawal (line 20) is added at one of the trays of the column. 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. On the Figure 2c , the tray (I) shown is the feed tray.

It can also be a plate located between the feed plate and the injection point of the stripping gas. 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.

In order to meet these criteria, 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).

For the description of the figure 2d , we will not describe again the references of figures 1 and 2c . The figure 2d represents an embodiment of the invention with the addition of a second lateral withdrawal at a plateau (II) different from the plateau (I).

According to figure 2d a part of the flow present at the level of at least one plate (II) located between the feed tray and the draw plate of the heavier 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. Preferably, 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.

In order to comply with these criteria, 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. In addition, 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.

All or part of the 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.

According to figure 2d , 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 step.

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.

As the examples below show, the embodiment of the figure 2d leads to better performance than the embodiment of the Figure 2c .

Description of the conditions of the hydrocracking step (2) and the separations:

This description refers to conventional conditions and implementations, which apply equally well to figures 1 and 2c (prior art) than the invention figure 2d ).

Charges :

A wide variety of 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. for desulphurization or hydroconversion in a fixed bed or a bubbling bed of RAT (atmospheric residues) and / or RSV (vacuum residues) and / or deasphalted oils, or the charge can be a deasphalted oil, effluents d a Fisher-Tropsch unit or any mixture of the aforementioned fillers. The above list is not exhaustive.

In general, 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). In the case of diesel, the T5 point is generally about 150 ° C. In the case of VGO, 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.

Guard Beds

In the case where the feedstock contains resins and / or asphaltenes-type compounds, it is advantageous to first pass the feedstock over a bed of catalyst or adsorbent other than the hydrocracking or hydrotreatment catalyst. 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. Preferably, the catalysts are impregnated with a hydro-dehydrogenation phase. Very preferably, the CoMo or NiMo phase is used. These catalysts may have macroporosity.

Operating conditions :

Operating conditions such as temperature, pressure, hydrogen recycling rate, hourly space velocity, may be very variable depending on the nature of the load, the quality of desired products and facilities available to the refiner. 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 6 h ^-1, more preferably between 0.2 and 3 h ^-1 and the quantity of hydrogen introduced being such that the volume ratio of liters of hydrogen / liter of hydrocarbon is between 80 and 5000 NI / I and most often between 100 and 3000 NI / I.

These operating conditions used in the hydrocracking processes generally make it possible to achieve pass conversions, converted products (ie with boiling points lower than the residual cutting point) greater than 15% and even more preferably between 20%. % and 95%.

The main objectives :

• hydrocraqueur maxi-naphta avec un point de coupe résidu généralement entre 150°C et 190°C, de préférence entre 160°C et 190°C, et le plus souvent de 170°C-180°C
• hydrocraqueur maxi-kérosène avec un point de coupe résidu généralement entre 240°C et 290°C, et le plus souvent de 260°C-280°C
• hydrocraqueur maxi diesel avec un point de coupe résidu généralement entre 340°C et 385°C, et le plus souvent de 360°C-380°C.

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 160 ° 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
• hydrocracker maxi diesel with a cutting point residue generally between 340 ° C and 385 ° C, and most often 360 ° C-380 ° C.

Modes of implementation :

The hydrocracking / hydroconversion processes using the catalysts according to the invention cover the pressure and conversion ranges from mild hydrocracking to high pressure hydrocracking.

By 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).

According to a first variant, 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. When the preferred products are the middle distillates, amorphous basic solids, for example alumina or silica-aluminas, are used. 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.

When gasoline is the predominantly desired product, 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) :

The separator (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.

Splitting (12)

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 counter-cyclically. 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.

EXAMPLES Example 1: Prior Art

This example is based on the configuration of the figure 1 . Two samples from an industrial unit in operation, based on the configuration of the figure 1 have been analyzed. The properties are reported in Table 1 below.

It should be noted that, in view of the configuration, the flows 15a, 16, 18 and 23 have exactly the same properties.

The splitting of the stream 11 in the column 12 was simulated by programming via the PRO / II software 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 operating conditions of the column used for the simulation are reported in Table 2 below.

From the properties of the input stream of the fractionation column (see Table 1), the simulation PRO / II could establish the properties of the output stream of the fractionation column, in particular the distribution in HPNA could be modeled.

Based on these results, the configurations of the invention were simulated. The results are set out below for each configuration 2c or 2d. <u> Table 1 </ u>: Flow properties according to the diagram of Figure 1 Configuration Flow of the Figure 1 Number of flows 11 15a 18 16 yield wt% 100 42 39.5 2.5 Quantity of diesel in the stream wt% 64.0 10.9 10.9 10.9 Sp gr 0.805 0.828 0.828 0.828 HPNA coronene ppm wt 209 four hundred ninety seven four hundred ninety seven four hundred ninety seven Dibenzo (e, phi) perylene ppm wt 33 78 78 78 Naphtho [8.2.1 abc] coronene ppm wt 81 192 192 192 ovalene ppm wt 57 135 135 135 Total HPNA ppm wt 378 902 902 902 TBP,% wt Initial boiling point ° C 128 200 200 200 10% ° C 200 368 368 368 50% ° C 326 402 402 402 90% ° C 440 477 477 477 Final boiling point ° C 524 524 524 524 1: relative density SG = ρ _sample at 20 ° C / ρ _H20 at 4 ° C where p is the density expressed in g / cm ³ Operating conditions of fractionation Figure 1 Column top pressure barg 1.0 Low column pressure barg 1.5 Input charge temperature ° C 377 Number of theoretical plateaus 34 Stripping steam flow kg of steam / ton of load 17

Example 2: Configuration 2c

Table 3 below gives the characteristics of the currents 11, 16 and 18 (identical to 20) in the configuration 2c resulting from the simulation PRO / II. The operating conditions of the column used for the simulation are shown in Table 4: <u> Table 3 </ u>: flow properties according to the diagram of figure 2c Configuration Flow of the Figure 2c Number of flows 11 entry 18 Liquid recycling 16 purge yield 100 39.5 2.5 Quantity of diesel in the stream 64.0 16.1 11.1 Sp gr 0.805 .8275 .8284 HPNA coronene 209 420 2153 Dibenzo (e, ghi) perylene 33 91 313 Naphtho [8.2.1 abc] coronene 81 121 873 ovalene 57 76 623 Total HPNA 378 707 3962 TBP,% wt Initial boiling point 128 89 207 10% 200 363 368 50% 326 399 402 90% 440 475 478 Final boiling point 524 524 524 1: relative density SG = ρ _sample at 20 ° C / ρ _H20 at 4 ° C where p is the density expressed in g / cm ³ Operating conditions of fractionation Figure 2c Column top pressure barg 1.0 Low column pressure barg 1.5 Input charge temperature ° C 377 Number of theoretical plateaus 34 Strippant steam flow kg of steam / ton of charge 17

Compared to the configuration of the figure 1 , the configuration 2c makes it possible to maximize the amount of HPNA (3962 ppm by weight to be compared with 902 ppm by weight of the configuration 1) in the unconverted fraction which is purged via the line 16. Together the amount of HPNA is minimized in the This stream flows 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%.

On the other hand, 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 18 but in addition that the proportion of heavy refractory and poisonous HPNA (Naphto [8.2,1 abc] coronene + Ovalene) is weaker.

Example 5: Configuration 2d

Table 5 below gives the characteristics of currents 11, 16 and 18 in the 2d configuration resulting from simulation PRO / II. The operating conditions of the column used for the simulation are shown in Table 6: <u> Table 5 </ u>: flow properties according to the diagram of figure 2d Configuration Flow of the figure 2d Number of flows 11 entry 18 Liquid recycling 16 purge yield 100 39.5 2.5 Quantity of diesel in the stream 64.0 6.8 4.0 Sp gr 0.805 .8273 .8338 HPNA coronene 209 405 2682 Dibenzo (e, ghi) perylene 33 106 379 Naphtho [8.2.1 abc] coronene 81 87 1106 ovalene 57 46 792 Total HPNA 378 644 4959 TBP,% wt Initial boiling point 128 78 298 10% 200 388 388 50% 326 399 442 90% 440 474 516 Final boiling point 524 524 524 1: relative density SG = ρ _sample at 20 ° C / ρ _H20 at 4 ° C where p is the density expressed in g / cm ³ Operating conditions of fractionation Figure 2d Column top pressure barg 1.0 Low column pressure barg 1.5 Input charge temperature ° C 377 Number of theoretical plateaus 34 Strippant steam flow kg of steam / ton of charge 17 Operating conditions of the lateral stripper Column top pressure barg 1.4 Low column pressure barg 1.5 Number of theoretical plateaus 6 Strippant steam flow kg of steam / ton of charge 28

Compared to the configuration of the figure 1 , the 2d configuration 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 line (16).

At the same time, 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. %.

On the other hand, 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.

In addition, 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.

Claims (13)

1. A process for hydrocracking an oil feed comprising at least 10% by volume of compounds boiling above 340°C, comprising a hydrocracking step, optionally followed by a separation of the gases from the hydrocracked effluent, then a step for fractionation of said effluent, which separates at least one distillate and a residue, , said fractionation step comprising a distillation in a column provided with plates, in which column:

   • said at least partially vaporized effluent is supplied to the column over at least one supply plate,

   • said distillate is withdrawn from the level of a withdrawal plate,

   • said residue is evacuated at an evacuation point,

   • and, a stripping gas is injected at an injection point located below the supply plate,
   in which process

   • a portion of the stream present at the level of at least one plate (I) which is the supply plate or a plate located, between the supply plate and said stripping gas injection point is withdrawn from the column,

   • all or a portion of said withdrawn stream is recycled to the hydrocracking step,

   • and the residue is purged in its entirety,

   in which a portion of the stream present at the level of at least one plate (II) located between the supply plate and the withdrawal plate for the heaviest distillate is withdrawn from the column, said at least one plate (II) being located above said supply plate ,
   in which all or a portion, preferably all, of said stream withdrawn from said plate (II) is stripped in an external stripping step by a stripping gas, and all or a portion, preferably all, of the separated gaseous effluent is recycled to the column above the plate from which said stream has been withdrawn, and all or a portion, preferably all, of the separated liquid effluent is recycled to the hydrocracking step.
2. The process as claimed in one of the preceding claims, in which said stream is withdrawn at the level of the supply plate or of a plate located below the supply plate and close to said supply plate, preferably at the level of the plate which is closest to the supply plate, is withdrawn from the column.
3. The process as claimed in one of the preceding claims, in which said withdrawn stream is recycled to the hydrocracking step directly or after optionally separating the gases, and preferably directly.
4. The process as claimed in one of the preceding claims, in which the stream withdrawn from the level of the plate (I) or the plate (II) has a concentration of HPNA of less than 500 ppm by weight, preferably less than 350 ppm by weight.
5. The process as claimed in one of the preceding claims, in which the stream withdrawn from the level of the plate (I) or the plate (II) has a proportion of at least 70% by weight of unconverted hydrocarbons, preferably at least 80% by weight of unconverted hydrocarbons.
6. The process as claimed in any preceding claims, in which all or a portion, preferably all, of said withdrawn stream is stripped in an external stripping step using a stripping gas, and all or a portion, preferably all, of the separated gaseous effluent is recycled to the column at the level of the plate closest to the plate from which said stream has been withdrawn.
7. The process as claimed in any preceding claims, in which the stripping gas injected into the external stripping step is steam, preferably at a pressure in the range 0.2 to 1.5 MPa.
8. The process as claimed in one of the preceding claims, in which a stripping gas is injected into the fractionation step, the gas preferably being steam, preferably at a pressure in the range 0.2 to 1.5 MPa.
9. A facility comprising:

   • a hydrocracking section (2) provided with an inlet line (1) for the feed and an inlet line (8) for hydrogen,

   • optionally followed by a zone (4) for separating effluent in order to separate a gaseous fraction,

   • followed by a fractionation section (12) comprising at least one distillation column provided with plates, said column comprising:

   ∘ at least one line (11) for the inflow of at least partially vaporized hydrocracked effluent onto at least one supply plate,

   ∘ at least one line (14) for withdrawing at least one distillate from the level of a withdrawal plate,

   ∘ at least one line (16) for evacuating as a purge the entirety of the residue,

   • and comprising at least one line (19) for injecting a stripping gas, the injection point being located below the supply plate,

   the facility further comprising:

   • at least one line (20) for withdrawing a portion of the stream present at the level of at least one plate (I) which is the supply plate or a plate between the supply plate and said stripping gas injection point,

   • at least one line (18) for recycling all or a portion of said withdrawn stream, preferably all, to the hydrocracking step,

   • at least one line (21) for withdrawing a portion of the stream present at the level of at least one plate (II) located between the supply plate and the plate for withdrawing the heaviest distillate fraction, said at least one plate (II) being located above the supply plate,

   • a stripper (25) external to the column, provided with an inlet line (21) for said withdrawn stream, a stripping gas injection line (26), an outlet line (22) for the gaseous fraction, an outlet line (23) for the liquid fraction,

   • a line (22) for recycling all or a portion, preferably all, of said gaseous fraction to said column, the line (22) discharging into the column above the plate from which said stream has been withdrawn,

   • a line (23) for recycling all or a portion, preferably all, of said liquid fraction to the hydrocracking step.
10. The facility as claimed in claim 9, comprising at least one line (18) for recycling said withdrawn stream in its entirety directly to the hydrocracking step.
11. The facility as claimed in claim 9 or claim 10, which does not comprise a line for recycling the liquid fraction separated in the stripping step to the fractionation column.
12. The facility as claimed in one of claims 9 to 11, which does not comprise a line for recycling residue to the column.
13. The facility as claimed in one of claims 9 to 12, comprises a line (22) discharging into the column above the plate (II) from which said stream has been withdrawn, at the level of the plate closest.

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