EP2158303B1 - Method for producing middle distillates by hydroisomerisation and hydrocracking of a heavy fraction from a fischer-tropsch effluent - Google Patents

Description

The present invention describes a process for the hydrocracking and hydroisomerization treatment of feedstocks from the Fischer-Tropsch process, making it possible to obtain middle distillates (gas oil, kerosene), ie initial boiling point cuts. at least 150 ° C and final at most 340 ° C and optionally oil bases.

In the Fischer-Tropsch process, the synthesis gas (CO + H ₂ ) is catalytically converted into oxygenates and substantially linear hydrocarbons in gaseous, liquid or solid form. However, these products, mainly made of normal paraffins, can not be used as such, in particular because of their cold-holding properties that are not very compatible with the usual uses of petroleum fractions. For example, the pour point of a linear hydrocarbon containing 20 carbon atoms per molecule (boiling point equal to about 340 ° C., ie often included in the middle distillate cut) is + 37 ° C. about which makes its use impossible, the specification being -15 ° C for diesel. Thus, the hydrocarbons from the Fischer-Tropsch process comprising mainly n-paraffins must be converted into more valuable products such as, for example, gas oil, kerosene, which are obtained, for example, after catalytic hydrocracking / hydroisomerization reactions. These products are generally free of heteroatomic impurities such as sulfur, nitrogen or metals. They contain practically no aromatics, naphthenes and more generally cycles, in particular in the case of cobalt catalysts.

On the other hand, they may have a significant content of unsaturated compounds of olefinic type and oxygenated products (such as alcohols, carboxylic acids, ketones, aldehydes and esters). These oxygenated and unsaturated compounds are more concentrated in the light fractions. Thus in the C5 + fraction corresponding to the products boiling at an initial boiling point of between 20 ° C. and 40 ° C., these compounds represent between 10-20% by weight of olefinic type unsaturated compounds and between 5-10% by weight. of oxygenated compounds.

One of the objectives of the invention is to eliminate, during a hydrotreatment step, upstream of a hydrocracking step, the olefinic type unsaturated compounds, said hydrotreatment step being carried out under less severe conditions. than those of the hydrocracking step. Unsaturated olefinic compounds present in the hydrocracking feeds reduce the service life of a hydrocracking catalyst. Indeed, under the severe hydrocracking / hydroisomerization operating conditions, the hydrogenation of the olefinic type unsaturated compounds being a strongly exothermic reaction, the transformation of the unsaturated compounds can have a negative impact on the hydroisomerization / hydrocracking step and cause, for example, a thermal runaway of the reaction, a large coking of the catalyst or the formation of gum by oligomerization.

One of the advantages of the invention is to provide a method for producing middle distillates from a paraffinic feedstock produced by Fischer Tropsch synthesis in which the hydrocracking step is preceded by a hydrogenation step allowing elimination previously and under less severe conditions than those used in the hydrocracking step, the most reactive elements and in particular unsaturated compounds of olefinic type.

State of the art

The Shell patent application ( EP-583.836 ) discloses a process for the production of middle distillates from a filler obtained by Fischer-Tropsch synthesis. In this process, the feedstock resulting from the Fischer-Tropsch synthesis can be treated in its entirety, but preferably the C4- fraction is withdrawn from the feedstock so that only the C5 + fraction boiling at a temperature above 20 ° C. be introduced in the subsequent step. Said feedstock is subjected to a hydrotreatment to hydrogenate the olefins and alcohols in the presence of a large excess of hydrogen, so that the conversion of products boiling above 370 ° C into products with a lower boiling point is less than 20%. The hydrotreated effluent consisting of high molecular weight paraffinic hydrocarbons is preferably separated from the hydrocarbon compounds having a low molecular weight and in particular the C4- fraction before the second hydroconversion stage. At least a portion of the remaining C5 + fraction is then subjected to a hydrocracking / hydroisomerization step with a conversion of products boiling above 370 ° C into products having a boiling point of at least 40% by weight.

The patent application US 2002/0169219 discloses a process for producing a C5-C20 cut from a paraffinic feedstock produced by Fischer Tropsch synthesis, however the feedstock undergoing the hydrotreatment and hydrocracking steps described in D1 results from a mixture of a fraction C5-C20 from the Fischer Tropsch process and a C5 + fraction containing sulfur from the fractionation of a natural gas source. The step of hydrotreating said feedstock is carried out at a temperature of between 204 and 482 ° C. and at a hydrogen flow rate corresponding to a hydrogen / hydrocarbon volume ratio of between 53.4 and 356 Nl / l / h. .

The patent GB 1,430,973 discloses a two-stage hydrocracking process of an aromatic charge comprising 20 to 70% by volume of aromatics and a boiling point between 221 and 537 ° C, in order to obtain a rich naphtha fraction in aromatic and a kerosene fraction with a low aromatic content. The hydrotreatment stage upstream of the hydrocracking stages operates at a temperature of between 287 and 454 ° C.

• de protéger le catalyseur d'hydroisomérisation / hydrocraquage des éléments les plus réactifs tels que les composés insaturés de type oléfinique par la mise en oeuvre en amont de l'étape d'hydroisomérisation / hydrocraquage, d'une étape d'hydrogénation des composés insaturés, l'élimination des composés insaturés de type oléfinique avant l'étape d'hydroisomérisation / hydrocraquage permettant d'éviter la formation de coke ou de gomme dans la zone d'hydroisomérisation / hydrocraquage,
• de faciliter le contrôle du profil de température à l'intérieur de la zone d'hydroisomérisation / hydrocraquage par la mise en oeuvre en amont de l'étape d'hydroisomérisation / hydrocraquage d'une étape d'hydrogénation des composés insaturés. L'hydrogénation des composés insaturés de type oléfiniques est en effet une réaction fortement exothermique qui peut avoir un impact négatif sur l'étape d'hydroisomérisation / hydrocraquage et provoquer par exemple un emballement thermique de la réaction dans le cas ou ces composés insaturés ne seraient pas éliminés en amont de l'étape d'hydroisomérisation / hydrocraquage,
• de mettre en oeuvre un procédé simplifié dans lequel la quantité d'hydrogène introduite dans la zone d'hydrogénation correspond à une quantité d'hydrogène en léger excès par rapport à la quantité strictement nécessaire pour réaliser la réaction d'hydrogénation des composés insaturés de type oléfinique de sorte que le procédé ne nécessite pas l'intégration d'un compresseur de recycle et que l'on ne réalise pas de craquage dans la zone d'hydrogénation. Ceci permet l'envoi direct, de préférence par pompage, de la totalité de l'effluent hydrogéné liquide, sans étape de séparation intermédiaire, dans la zone d'hydroisomérisation / hydrocraquage, ainsi que l'utilisation d'une quantité d'hydrogène considérablement réduite.
• d'améliorer fortement les propriétés à froid des paraffines issues du procédé Fisher-Tropsch et ayant des points d'ébullition correspondants à ceux des fractions gazole et kérosène, (encore appelées distillats moyens) et notamment d'améliorer le point de congélation des kérosènes.
• d'augmenter la quantité de distillats moyens disponibles par hydrocraquage des composés paraffiniques les plus lourds, présents dans l'effluent de sortie de l'unité Fischer-Tropsch, et qui ont des points d'ébullition supérieurs à ceux des coupes kérosène et gazole, par exemple la fraction 370°C+.

The present invention provides an alternative process for the production of middle distillates. The advantages of the present invention are:

• to protect the hydroisomerization / hydrocracking catalyst from the most reactive elements such as the olefinic type unsaturated compounds by carrying out, upstream of the hydroisomerization / hydrocracking step, a step of hydrogenation of the unsaturated compounds, the elimination of olefinic unsaturated compounds before the hydroisomerization / hydrocracking step to avoid the formation of coke or gum in the hydroisomerization / hydrocracking zone,
• to facilitate the control of the temperature profile inside the hydroisomerization / hydrocracking zone by the upstream implementation of the hydroisomerization / hydrocracking step of a hydrogenation step of the unsaturated compounds. The hydrogenation of the olefinic type unsaturated compounds is in fact a strongly exothermic reaction which may have a negative impact on the hydroisomerization / hydrocracking step and cause, for example, a thermal runaway of the reaction in the case where these unsaturated compounds are not not removed upstream of the hydroisomerization / hydrocracking step,
• to implement a simplified process in which the amount of hydrogen introduced into the hydrogenation zone corresponds to a quantity of hydrogen in slight excess with respect to the quantity strictly necessary to carry out the hydrogenation reaction of the unsaturated compounds of type olefinic so that the process does not require the integration of a recycle compressor and that no cracking is carried out in the hydrogenation zone. This allows the direct sending, preferably by pumping, of all the liquid hydrogenated effluent, without intermediate separation step, in the hydroisomerization / hydrocracking zone, as well as the use of a quantity of hydrogen considerably. scaled down.
• to strongly improve the cold properties of paraffins from the Fisher-Tropsch process and having boiling points corresponding to those of diesel and kerosene fractions (also called middle distillates) and in particular to improve the freezing point of kerosines.
• to increase the amount of available middle distillates by hydrocracking the heavier paraffinic compounds present in the outlet effluent of the Fischer-Tropsch unit, and which have boiling points higher than those of the kerosene and diesel fractions, for example the fraction 370 ° C +.

1. a) séparation d'au moins une fraction gazeuse C4-, dite légère, à point d'ébullition final inférieur à 20°C, de l'effluent issu de l'unité de synthèse Fischer Tropsch de façon à obtenir une seule fraction liquide C5+, dite lourde, à point d'ébullition initial compris entre 20 et 40°C,
2. b) hydrogénation des composés insaturés de type oléfiniques d'au moins une partie de ladite fraction lourde C5+, en présence d'hydrogène et d'un catalyseur d'hydrogénation à une température comprise entre 100°C et 180 °C, à une pression totale comprise entre 0,5 et 6 MPa, à une vitesse volumique horaire comprise entre 1 et 10h-1, et à un débit d'hydrogène correspondant à un rapport volumique hydrogène/hydrocarbures compris entre 10 et 50 Nl/l/h,
3. c) hydroisomérisation/hydrocraquage de la totalité de l'effluent hydrogéné liquide issu de l'étape b), sans étape de séparation préalable, en présence d'hydrogène et d'un catalyseur d'hydroisomérisation/hydrocraquage,
4. d) distillation de l'effluent hydrocraqué / hydroisomérisé.

The figure 1 represents the embodiment of the method according to the largest invention. More specifically, the figure 1 represents a process for producing middle distillates from a paraffinic feedstock produced by Fischer-Tropsch synthesis, comprising the following successive steps:

1. a) separation of at least one C4- gas fraction, so-called mild, with a final boiling point below 20 ° C, from the effluent from the Fischer Tropsch synthesis unit so as to to obtain a single C5 + liquid fraction, so-called heavy, with an initial boiling point of between 20 and 40 ° C,
2. b) hydrogenating the olefinically unsaturated compounds of at least a portion of said C5 + heavy fraction, in the presence of hydrogen and a hydrogenation catalyst at a temperature between 100 ° C and 180 ° C, at a pressure of total of between 0.5 and 6 MPa, at an hourly space velocity of between 1 and 10 h -1, and at a hydrogen flow rate corresponding to a hydrogen / hydrocarbon volume ratio of between 10 and 50 Nl / l / h,
3. c) hydroisomerization / hydrocracking of all the liquid hydrogen effluent from step b), without prior separation step, in the presence of hydrogen and a hydroisomerization / hydrocracking catalyst,
4. d) distillation of the hydrocracked / hydroisomerized effluent.

Detailed description of the invention

Throughout the remainder of the description, we will detail the various steps of the method according to the invention with reference to the figures 2 and 3 which represent preferred embodiments of the method according to the invention without limiting the scope thereof.

Step (a)

Step a) according to the invention, not shown on the figure 1 is a step of separation of at least one C4- fraction, called light, with a final boiling point of less than 20 ° C, preferably less than 10 ° C and very preferably less than 0 ° C, of the effluent resulting from the Fischer Tropsch synthesis so as to obtain a single C5 + fraction, so-called heavy, with an initial boiling point of between 20 and 40 ° C and preferably having a boiling point greater than or equal to 30 ° C , constituting at least a part of the charge of the hydrogenation step b) according to the invention.

The effluent from the Fischer-Tropsch synthesis unit is, at the outlet of the Fischer-Tropsch synthesis unit advantageously divided into two fractions, a light fraction, called cold condensate, (line (1)) and a fraction heavy, called waxes, (pipe (3)).

The two fractions thus defined comprise water, carbon dioxide (CO ₂ ), carbon monoxide (CO) and unreacted hydrogen (H ₂ ). In addition, the light fraction, cold condensate, contains light hydrocarbon compounds C1 to C4, called C4- fraction, in the form of gas.

According to a preferred embodiment shown in the figure 2 the light fraction, called cold condensate (1), and the heavy fraction, called waxes (3), are separately treated in separate fractionation means and then recombined in line (5), so as to obtain a single C5 + fraction. , said heavy, initial boiling point between 20 and 40 ° C and preferably having a boiling temperature greater than or equal to 30 ° C. The heavy fraction, called waxes, enters a fractionation means (4) via line (3). The fractionation means (4) may for example consist of methods well known to those skilled in the art such as rapid expansion (or flash, according to the English terminology), distillation or stripping. Advantageously, a flash or flash tank or a stripper is sufficient to remove most of the water, carbon dioxide (CO ₂ ) and carbon monoxide (CO) through the line (4 ') of the heavy fraction, called waxes.

The light fraction, called cold condensate, enters a fractionation means (2) via the pipe (1). The fractionation means (2) may for example consist of methods well known to those skilled in the art such as a flash or flash tank, distillation or stripping. Advantageously, the fractionation means (2) is a distillation column allowing the elimination of the light and gaseous hydrocarbon compounds C1 to C4, called gas fraction C4-, corresponding to products boiling at a temperature below 20 ° C, preferably below at 10 ° C and very preferably, below 0 ° C, through the pipe (2 ').

The stabilized effluents from the fractionation means (2) and (4) are then recombined in the pipe (5). A stabilized C5 + liquid fraction, corresponding to products boiling at an initial boiling point of between 20 and 40 ° C. and preferably having a boiling point greater than or equal to 30 ° C., is thus recovered in the pipe (5) and constitutes the charge of the hydrogenation step b) of the process according to the invention.

According to another preferred embodiment shown in the figure 3 the light fraction, called cold condensate, leaving the Fischer-Tropsch synthesis unit via line (1) and the heavy fraction, called waxes, leaving the Fischer-Tropsch synthesis unit via line (3) , are recombined in the pipe (18) and treated in the same fractionation means (4). The fractionation means (4) may for example consist of methods well known to those skilled in the art such as flash, distillation or stripping. Advantageously, the fractionation means (4) is a distillation column allowing the removal of the gas fraction C4-, water, carbon dioxide (CO ₂ ) and carbon monoxide (CO) through the pipe (4 ').

A stabilized C5 + liquid fraction, corresponding to the products boiling at a boiling point of between 20 and 40 ° C. and preferably having a boiling point greater than or equal to 30 ° C., is thus recovered at the outlet of the fractionation means (4). ) in the pipe (5) and constitutes the charge of the hydrogenation step b) of the process according to the invention.

Step b)

Step b) of the process according to the invention is a step of hydrogenation of the olefinic type unsaturated compounds of at least a part and preferably of the whole of the C5 + heavy liquid fraction resulting from step a) of the process according to the invention, in the presence of hydrogen and a hydrogenation catalyst.

Said C5 + liquid heavy fraction is admitted in the presence of hydrogen (line 6) in a hydrogenation zone (7) containing a hydrogenation catalyst which aims to saturate the unsaturated olefinic compounds present in the C5 + heavy liquid fraction. described above.

Preferably, the catalyst used in step (b) according to the invention is a non-crunchy or slightly cracking hydrogenation catalyst comprising at least one metal of group VIII of the periodic table of the elements and comprising at least one carrier with refractory oxide base.

Preferably, said catalyst comprises at least one group VIII metal chosen from nickel, molybdenum, tungsten, cobalt, ruthenium, indium, palladium and platinum and comprising at least one oxide-based support refractory selected from alumina and silica alumina.

Preferably, the Group VIII metal is chosen from nickel, palladium and platinum.

According to a preferred embodiment of step b) of the process according to the invention, the group VIII metal is chosen from palladium and / or platinum and the content of this metal is advantageously between 0.1% and 5%. % by weight, and preferably between 0.2% and 0.6% by weight relative to the total weight of the catalyst.

According to a very preferred embodiment of step b) of the process according to the invention, the Group VIII metal is palladium.

According to another preferred embodiment of step b) of the process according to the invention, the metal of group VIII is nickel and the content of this metal is advantageously between 5% and 25% by weight, preferably between 7%. and 20% by weight based on the total weight of the catalyst.

The catalyst support used in step (b) of the process according to the invention is a refractory oxide-based support, preferably chosen from alumina and silica-alumina.

When the support is an alumina, it has a BET specific surface to limit the polymerization reactions on the surface of the hydrogenation catalyst, said surface being between 5 and 140 m ² / g.

When the support is a silica-alumina, the support contains a percentage of silica of between 5 and 95% by weight, preferably between 10 and 80%, more preferably between 20 and 60% and very preferably between 30 and 50%. a BET specific surface area of between 100 and 550 m ² / g, preferably between 150 and 500 m ² / g, preferably less than 350 m ² / g and even more preferably less than 250 m ² / g ,

The hydrogenation stage b) of the process according to the invention is preferably carried out in one or more fixed bed reactor (s).

In the hydrogenation zone (7), the feedstock is brought into contact with the hydrogenation catalyst in the presence of hydrogen and at operating temperatures and pressures allowing the hydrogenation of the olefinic unsaturated compounds present in the feedstock. Under these operating conditions, the oxygenated compounds are not converted, the liquid hydrogen effluent from step b) of the process according to the invention therefore does not contain water resulting from the conversion of said oxygenated compounds.

According to the invention, the operating conditions of the hydrogenation stage b) are chosen so that the effluent leaving said hydrogenation zone (7) is in the liquid state: indeed, the amount of hydrogen introduced into the hydrogenation zone (7) corresponds to a quantity of hydrogen in slight excess with respect to the quantity of hydrogen strictly necessary to carry out the hydrogenation reaction of the unsaturated compounds of the type olefin. Thus, no cracking is carried out in the hydrogenation zone (7), and the liquid hydrogenated effluent does not contain hydrocarbon compounds boiling at a temperature below 20 ° C., preferably below 10 ° C. and very preferred, lower than 0 ° C, corresponding to the gaseous fraction C4-.

The operating conditions of the hydrogenation step b) of the process according to the invention are the following: the temperature within said hydrogenation zone (7) is between 100 and 180 ° C. and preferably between 120 and 180 ° C. and 165 ° C, the total pressure is between 0.5 and 6 MPa, preferably between 1 and 5 MPa and even more preferably between 2 and 5 MPa. The feedstock flow rate is such that the hourly space velocity (ratio of the hourly flow rate at 15 ° C of liquid fresh feed over the catalyst volume loaded) is between 1 and 10 h ^-1, preferably between 1 and 5 h ^-1 and even more preferably between 1 and 4 h ^-1 . The hydrogen that feeds the hydrotreating zone is introduced at a rate such that the volume ratio hydrogen / hydrocarbons is between 10 and 50 Nl / l / h, and preferably between 15 and 35 Nl / l / h.

Under these conditions, the olefinic type unsaturated compounds are hydrogenated more than 50%, preferably more than 75% and preferably more than 85%.

The hydrogenation step b) of the process according to the invention is preferably carried out under conditions such as conversion to products having boiling points greater than or equal to 370 ° C in products having lower boiling points. at 370 ° C is zero. The hydrogenated effluent from step b) of the process according to the invention therefore does not contain compounds boiling at a temperature below 20 ° C, preferably below 10 ° C and very preferably below 0 ° C C, corresponding to the gas fraction C4-.

According to a preferred embodiment of step b) of the process according to the invention, use is made of a guard bed (not shown in the figures) containing at least one guard bed catalyst upstream of the hydrogenation zone ( 7) to reduce the content of solid mineral particles and possibly reduce the content of harmful metal compounds for hydrogenation catalysts. The guard bed may advantageously be either integrated in the hydrogenation zone (7) upstream of the hydrogenation catalyst bed or be placed in a separate zone upstream of the hydrogenation zone (7).

Indeed, the treated fractions may optionally contain solid particles such as inorganic solids. They may optionally contain metals contained in hydrocarbon structures such as more or less soluble organometallic compounds. By the term fines is meant fines resulting from a physical or chemical attrition of the catalyst. They can be micron or sub-micron. These mineral particles then contain the active components of these catalysts without the following list being limiting: alumina, silica, titanium, zirconia, cobalt oxide, iron oxide, tungsten, rhuthenium oxide, etc. These solid minerals may be present under the calcined mixed oxide form: for example, alumina-cobalt, alumina-iron, alumina-silica, alumina-zirconia, alumina-titanium, alumina-silica-cobalt, alumina-zirconia-cobalt, ....

They may also contain metals within hydrocarbon structures, which may optionally contain oxygen or more or less soluble organometallic compounds. More particularly, these compounds may be based on silicon. It may be for example anti-foaming agents used in the synthesis process. On the other hand, the catalyst fines described above may have a higher silica content than the catalyst formulation resulting from the intimate interaction between the catalyst fines and anti-foaming agents described above.

The guard bed catalysts used may advantageously be 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.

In order to overcome the presence of contaminants and / or poisons in the feed, the bed bed catalysts may, in another preferred embodiment, have more specific 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. Among the particular forms possible without this list being exhaustive: hollow cylinders, hollow rings, Raschig rings, serrated hollow cylinders, crenellated hollow cylinders, pentaring carts, multi-hole cylinders ...

Preferably, said guard bed catalysts used are not impregnated with an active phase. Guard beds can be marketed by Norton-Saint-Gobain, for example example MacroTrap® guard beds. Guard beds can be marketed by Axens in the ACT family: ACT077, ACT935, ACT961 or HMC841, HMC845, HMC941 or HMC945. It may be particularly advantageous to superpose these catalysts in at least two different beds of varying heights. 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. These guard bed catalysts used may advantageously have macroporosity. In a preferred embodiment, the macroporous volume for a mean diameter at 50 nm is greater than 0.1 cm ³ / g and a total volume greater than 0.60 cm ³ / g. In another embodiment, the mercury volume for a pore diameter greater than 1 micron is greater than 0.5 cm ³ / g and the mercury volume for a pore diameter greater than 10 microns is greater than 0.25 cm ³ /boy Wut. These two embodiments can advantageously be associated in a mixed bed or a combined bed. The preferred guard beds according to the invention are HMC and ACT961.

After passing over the guard bed, the solids content is advantageously less than 20 ppm, preferably less than 10 ppm and even more preferably less than 5 ppm. The soluble silicon content is advantageously less than 5 ppm, preferably less than 2 ppm and even more preferably less than 1 ppm.

At the end of step b) of the process according to the invention, all the liquid hydrogenated effluent is directly sent to a hydrocracking / hydroisomerization zone (10).

Step c)

According to step c) of the process according to the invention, the totality of the liquid hydrogenated effluent resulting from step b) of the process according to the invention is directly sent, without prior separation step, to the zone of hydroisomerization / hydrocracking (10) containing the hydroisomerization / hydrocracking catalyst and preferably at the same time as a hydrogen stream (line 9).

• La pression est généralement maintenue entre 0,2 et 15 MPa et de préférence entre 0,5 et 10 MPa et avantageusement de 1 à 9 MPa, la vitesse spatiale est généralement comprise entre 0,1 h-1 et 10 h-1 et de préférence entre 0,2 et 7 h-1 est avantageusement entre 0,5 et 5,0 h-1. Le taux d'hydrogène est généralement compris entre 100 et 2000 Normaux litres d'hydrogène par litre de charge et par heure et préférentiellement entre 150 et 1500 litres d'hydrogène par litre de charge.

The operating conditions in which the hydroisomerization / hydrocracking step (c) of the process according to the invention is carried out are preferably as follows:

• The pressure is generally maintained between 0.2 and 15 MPa and preferably between 0.5 and 10 MPa and advantageously from 1 to 9 MPa, the space velocity is generally comprised between 0.1 h -1 and 10 h -1 and preferably between 0.2 and 7 h -1 is advantageously between 0.5 and 5.0 h -1. The hydrogen content is generally between 100 and 2000 normal liters of hydrogen per liter of filler and per hour and preferably between 150 and 1500 liters of hydrogen per liter of filler.

The temperature used in this step is generally between 200 and 450 ° C. and preferably from 250 ° C. to 450 ° C., advantageously from 300 to 450 ° C., and even more advantageously above 320 ° C. or for example between 320 ° -420 ° C. vs.

The hydroisomerization and hydrocracking step c) of the process according to the invention is advantageously carried out under conditions such that the pass conversion into products with boiling points greater than or equal to 370 ° C. into products having points. boiling point below 370 ° C. is greater than 80% by weight, and even more preferably at least 85%, preferably greater than 88%, so as to obtain middle distillates (gas oil and kerosene) having sufficiently good cold (pour point, freezing point) to meet the specifications in force for this type of fuel.

The hydroisomerization / hydrocracking catalysts

The majority of catalysts currently used in hydroisomerization / hydrocracking are of the bifunctional type associating an acid function with a hydrogenating function. The acid function is generally provided by supports with large surface areas (150 to 800 m2.g-1 generally) having a surface acidity, such as halogenated aluminas (chlorinated or fluorinated in particular), phosphorus aluminas, combinations of oxides of boron and aluminum, silica aluminas. The hydrogenating function is generally provided either by one or more metals of group VIII of the periodic table of the elements, such as iron, cobalt, nickel, ruthenium, rhodium, palladium, osmium, iridium and platinum, or by an association of at least a Group VI metal such as chromium, molybdenum and tungsten and at least one Group VIII metal.

In the case of bi-functional catalysts, the equilibrium between the two acid and hydrogenating functions is the fundamental parameter which governs the activity and the selectivity of the catalyst. A weak acidic function and a strong hydrogenating function give catalysts which are not very active and selective towards isomerization whereas a strong acid function and a low hydrogenating function give very active and cracking-selective catalysts. A third possibility is to use a strong acid function and a strong hydrogenating function to obtain a very active catalyst but also very selective towards isomerization. It is therefore possible, judiciously choosing each of the functions to adjust the activity / selectivity of the catalyst.

Advantageously, the hydroisomerization-hydrocracking catalysts are bifunctional catalysts comprising an amorphous acid support (preferably a silica-alumina) and a hydro-dehydrogenating metal function preferably provided by at least one noble metal. The support is said to be amorphous, that is to say devoid of molecular sieves, and in particular of zeolite, as well as the catalyst. The amorphous acidic support is advantageously a silica-alumina but other supports are usable. When it is a silica-alumina, the catalyst preferably does not contain added halogen, other than that which could be introduced for the impregnation of the noble metal, for example.

More generally, and preferably, the catalyst does not contain added halogen, for example fluorine. In general, and preferably, the support has not been impregnated with a silicon compound.

• une teneur pondérale en silice SiO₂ comprise entre 5 et 95% de préférence entre 10 et 80%, de manière plus préférée, entre 20 et 60% et de manière encore plus préférée entre 30 et 50% poids.
• une teneur en Na inférieure à 300 ppm poids et de préférence inférieure à 200 ppm poids,
• un volume poreux total compris entre 0,45 et 1,2 ml/g mesuré par porosimétrie au mercure,
• la porosité de ladite silice-alumine étant la suivante :
  1. i/ Le volume des mésopores dont le diamètre est compris entre 40Å et 150Å, et dont le diamètre moyen varie entre 80 et 140 Å et de préférence entre 80 et 120 A, représente entre 20 et 80% du volume poreux total mesuré par porosimétrie au mercure,
  2. ii/ Le volume des macropores, dont le diamètre est supérieur à 500 Å, et de préférence compris entre 1000 Å et 10000 Å représente entre 20 et 80% du volume poreux total mesuré par porosimétrie au mercure,
• une surface spécifique comprise entre 100 et 550 m²/g, de préférence comprise entre 150 et 500 m²/g, de manière préférée inférieure à 350 m²/g et de manière encore plus préférée, inférieure à 250 m²/g.

A preferred hydroisomerization / hydrocracking catalyst used in step c) of the process according to the invention comprises up to 3% by weight of metal of at least one hydro-dehydrogenating element chosen from noble metals of group VIII, preferably deposited on the support, and very preferably, the noble metal of group VIII being platinum and a support comprising (or preferably consisting of) at least one silica-alumina, said silica-alumina having the following characteristics:

• a weight content of silica SiO ₂ of between 5 and 95%, preferably between 10 and 80%, more preferably between 20 and 60% and even more preferably between 30 and 50% by weight.
• an Na content of less than 300 ppm by weight and preferably less than 200 ppm by weight,
• a total pore volume of between 0.45 and 1.2 ml / g measured by mercury porosimetry,
• the porosity of said silica-alumina being as follows:
  1. The volume of the mesopores whose diameter is between 40Å and 150Å, and whose mean diameter varies between 80 and 140 Å and preferably between 80 and 120 A, represents between 20 and 80% of the total pore volume measured by porosimetry at mercury,
  2. ii / The volume of the macropores, whose diameter is greater than 500 Å, and preferably between 1000 Å and 10000 Å, represents between 20 and 80% of the total measured pore volume by mercury porosimetry,
• a specific surface area of between 100 and 550 m ² / g, preferably between 150 and 500 m ² / g, preferably less than 350 m ² / g and even more preferably less than 250 m ² / g.

• un diamètre moyen poreux, mesuré par porosimétrie au mercure, compris entre 20 et 140 Å,
• un volume poreux total, mesuré par porosimétrie au mercure, compris entre 0,1 ml/g et 0,5 ml/g,
• un volume poreux total, mesuré par porosimétrie azote, compris entre 0,1 ml/g et 0,6 ml/g,
• une surface spécifique BET comprise entre 100 et 550 m²/g,
• un volume poreux, mesuré par porosimétrie au mercure, compris dans les pores de diamètre supérieur à 140 Å inférieur à 0,1 ml/g,
• un volume poreux, mesuré par porosimétrie au mercure, compris dans les pores de diamètre supérieur à 160 Å inférieur à 0,1 ml/g,
• un volume poreux, mesuré par porosimétrie au mercure, compris dans les pores de diamètre supérieurs à 200 Å, inférieur à 0,1 ml/g,
• un volume poreux, mesuré par porosimétrie au mercure, compris dans les pores de diamètre supérieurs à 500 Å inférieur à 0,1 ml/g.
• un diagramme de diffraction X qui contient au moins les raies principales caractéristiques d'au moins une des alumines de transition comprise dans le groupe composé par les alumines alpha, rhô, chi, eta, gamma, kappa, thêta et delta.
• une densité de remplissage tassée des catalyseurs supérieure à 0,55 g/cm³. Avantageusement, les caractéristiques associées au catalyseur correspondant sont identiques à celles de la silice alumine décrite ci-dessus.

A second preferred hydroisomerization / hydrocracking catalyst used in stage c) of the process according to the invention comprises up to 3% by weight of metal of at least one hydro-dehydrogenating element chosen from the noble metals of group VIII of the periodic classification and preferably the noble metal of group VIII being platinum, from 0.01 to 5.5% by weight of oxide of a doping element selected from phosphorus, boron and silicon and a non-zeolitic support to silica - alumina base containing an amount greater than 15% by weight and less than or equal to 95% by weight of silica (SiO ₂ ), said silica - alumina having the following characteristics:

• a mean pore diameter, measured by mercury porosimetry, of between 20 and 140 Å,
• a total pore volume, measured by mercury porosimetry, of between 0.1 ml / g and 0.5 ml / g,
• a total pore volume, measured by nitrogen porosimetry, of between 0.1 ml / g and 0.6 ml / g,
• a BET specific surface area of between 100 and 550 m ² / g,
• a porous volume, measured by mercury porosimetry, included in pores with a diameter greater than 140 Å of less than 0.1 ml / g,
• a porous volume, measured by mercury porosimetry, included in pores with a diameter greater than 160 Å less than 0.1 ml / g,
• a porous volume, measured by mercury porosimetry, included in pores with diameters greater than 200 Å, less than 0.1 ml / g,
• a porous volume, measured by mercury porosimetry, included in pores with diameters greater than 500 Å less than 0.1 ml / g.
• an X-ray diffraction pattern which contains at least the principal characteristic lines of at least one of the transition aluminas included in the group consisting of alpha, rho, chi, eta, gamma, kappa, theta and delta alumina.
• a packed packing density of the catalysts greater than 0.55 g / cm ³ . Advantageously, the characteristics associated with the corresponding catalyst are identical to those of the silica alumina described above.

The two stages b) and c) of the process according to the invention, hydrogenation and hydroisomerization-hydrocracking, can advantageously be carried out on the two types of catalysts in two or more different reactors, and / or in the same reactor.

• alumine contenant une quantité supérieure à 15% poids et inférieure ou égale à 95% poids de silice (SiO₂), de préférence une quantité supérieure à 15% poids et inférieure ou égale à 50% poids de silice, ladite silice - alumine présentant les caractéristiques suivantes :
• un diamètre moyen poreux, mesuré par porosimétrie au mercure, compris entre 20 et 140 Å,
• un volume poreux total, mesuré par porosimétrie au mercure, compris entre 0,1 ml/g et 0,5 ml/g,
• un volume poreux total, mesuré par porosimétrie azote, compris entre 0,1 ml/g et 0,6 ml/g,
• une surface spécifique BET comprise entre 100 et 550 m²/g,
• un volume poreux, mesuré par porosimétrie au mercure, compris dans les pores de diamètre supérieur à 140 Å inférieur à 0,1 ml/g,
• un volume poreux, mesuré par porosimétrie au mercure, compris dans les pores de diamètre supérieur à 160 Å inférieur à 0,1 ml/g,
• un volume poreux, mesuré par porosimétrie au mercure, compris dans les pores de diamètre supérieurs à 200 Å, inférieur à 0,1 ml/g,
• un volume poreux, mesuré par porosimétrie au mercure, compris dans les pores de diamètre supérieurs à 500 Å inférieur à 0,1 ml/g.
• un diagramme de diffraction X qui contient au moins les raies principales caractéristiques d'au moins une des alumines de transition comprise dans le groupe composé par les alumines alpha, rhô, chi, eta, gamma, kappa, thêta et delta.
• une densité de remplissage tassée des catalyseurs supérieure à 0,55 g/cm³.

A third preferred hydroisomerization / hydrocracking catalyst used in step c) of the process according to the invention comprises at least one hydro-dehydrogenating element chosen from the non-noble metals of group VIII and the metals of group VIB of the periodic table, preferably between 2.5 and 5% by weight of Group VIII non-noble elemental oxide and between 20 and 35% by weight of Group VIB element oxide with respect to the weight of the final catalyst and, preferably, the non-noble metal of group VIII is nickel and the metal of group VIB is tungsten, optionally from 0.01 to 5.5% by weight of oxide of a doping element chosen from phosphorus, boron and silicon and preferably, from 0.01 to 2.5% by weight of oxide of a doping element and a non-zeolitic silica-based support.

• alumina containing an amount greater than 15% by weight and less than or equal to 95% by weight of silica (SiO ₂ ), preferably an amount greater than 15% by weight and less than or equal to 50% by weight of silica, said silica-alumina exhibiting the following characteristics:
• a mean pore diameter, measured by mercury porosimetry, of between 20 and 140 Å,
• a total pore volume, measured by mercury porosimetry, of between 0.1 ml / g and 0.5 ml / g,
• a total pore volume, measured by nitrogen porosimetry, of between 0.1 ml / g and 0.6 ml / g,
• a BET specific surface area of between 100 and 550 m ² / g,
• a porous volume, measured by mercury porosimetry, included in pores with a diameter greater than 140 Å of less than 0.1 ml / g,
• a porous volume, measured by mercury porosimetry, included in pores with a diameter greater than 160 Å less than 0.1 ml / g,
• a porous volume, measured by mercury porosimetry, included in pores with diameters greater than 200 Å, less than 0.1 ml / g,
• a porous volume, measured by mercury porosimetry, included in pores with diameters greater than 500 Å less than 0.1 ml / g.
• an X-ray diffraction pattern which contains at least the principal characteristic lines of at least one of the transition aluminas included in the group consisting of alpha, rho, chi, eta, gamma, kappa, theta and delta alumina.
• a packed packing density of the catalysts greater than 0.55 g / cm ³ .

Advantageously, the characteristics associated with the corresponding catalyst are identical to those of the silica alumina described above.

When the third preferred hydroisomerization / hydrocracking catalyst is used in step c) of the process according to the invention, said catalyst is sulphurized.

According to a first preferred embodiment of the process according to the invention, a palladium-containing catalyst is used in the hydrogenation step b) and in the hydroisomerization / hydrocracking step c), a platinum-containing catalyst.

According to a second preferred embodiment of the process according to the invention, a palladium-containing catalyst is used in the hydrogenation step b) and in the hydroisomerization / hydrocracking step c), a sulphurized catalyst containing at least one hydro-dehydrogenating element selected from Group VIII non-noble metals and Group VIB metals.

According to a third preferred embodiment of the process according to the invention, in the hydrogenation step b), a catalyst containing at least one non-noble hydro-dehydrogenating element of group VIII and in step c) of hydroisomerization is used. hydrocracking, a sulphurized catalyst containing at least one hydro-dehydrogenating element chosen from Group VIII non-noble metals and Group VIB metals.

Step (d)

The effluent (so-called hydrocracked / hydroisomerized fraction) leaving the hydroisomerization / hydrocracking zone (10), resulting from step (c) of the process according to the invention, is sent, in accordance with step d) of process according to the invention, in a distillation train (11), which incorporates an atmospheric distillation and optionally a vacuum distillation, which aims to separate the conversion products of boiling point below 340 ° C and preferably less than 370 ° C and including in particular those formed during step (c) in the hydroisomerization / hydrocracking reactor (10), and to separate the residual fraction whose initial boiling point is generally greater than at least 340 ° C and preferably greater than or equal to at least 370 ° C. Among the conversion products and hydroisomerized, it is separated in addition to the light gases C1-C4 (line 12) at least one gasoline fraction (or naphtha) (line 13), and at least one middle distillate fraction kerosene (line 14) and diesel (line 15). Preferably, the residual fraction, whose initial boiling point is generally greater than at least 340 ° C and preferably greater than or equal to at least 370 ° C is recycled (line 16) in step c) of the process according to the invention at the head of the zone (10) for hydroisomerization and hydrocracking. According to another embodiment of step d) of the process according to the invention, said residual fraction can provide excellent bases for the oils.

It may also be advantageous to recycle (line 17) at least partly and preferably completely, in step (c) (zone 10) at least one of the kerosene and diesel fuel cuts thus obtained. The gas oil and kerosene cuts are preferably recovered separately or mixed, but the cutting points are adjusted by the operator according to his needs. It has been found that it is advantageous to recycle a portion of the kerosene to improve its cold properties.

The products obtained

The gas oil (s) obtained has a pour point of at most 0 ° C, generally below -10 ° C and often below -15 ° C. The cetane number is greater than 60, generally greater than 65, often greater than 70.

The resulting kerosene (s) has a freezing point of not more than -35 ° C, generally less than -40 ° C. The smoke point is greater than 25 mm, usually greater than 30 mm. In this process, the production of gasoline (not sought) is as low as possible. The yield of gasoline is always less than 50% by weight, preferably less than 40% by weight, advantageously less than 30% by weight or 20% by weight or even 15% by weight.

Claims (14)

1. A process for producing middle distillates from a paraffinic feed produced by Fischer-Tropsch synthesis, comprising the following steps in succession :

   a) separating at least one gaseous C4- fraction, termed the light fraction, with an end boiling point of less than 20°C, from the effluent derived from the Fischer-Tropsch synthesis unit to obtain a single C5+ liquid fraction, termed the heavy fraction, with an initial boiling point in the range 20°C to 40°C;

   b) hydrogenating the unsaturated olefinic type compounds of at least a portion of said heavy fraction C5+, in the presence of hydrogen and a hydrogenation catalyst at a temperature in the range 100°C to 180°C, at a total pressure in the range 0.5 to 6 MPa, at an hourly space velocity in the range 1 to 10 h^-1 , and at a hydrogen flow rate corresponding to a hydrogen/hydrocarbons volume ratio in the range 10 to 50 NI/I/h;

   c) hydroisomerizing/hydrocracking the entire liquid hydrogenated effluent from step b) with no prior separation step in the presence of hydrogen and a hydroisomerization/hydrocracking catalyst;

   d) distilling the hydrocracked/hydroisomerized effluent.
2. A process according to claim 1, in which, at the outlet from the Fischer-Tropsch synthesis unit, said effluent from the Fischer-Tropsch synthesis unit is divided into two fractions, a light fraction termed the cold condensate, and a heavy fraction termed the waxes.
3. A process according to claim 2, in which the light fraction, termed the cold condensate, and the heavy fraction, termed the waxes, are treated separately in separate fractionation means then re-combined, to obtain a single C5+ fraction, termed the heavy fraction, with an initial boiling point in the range 20°C to 40°C.
4. A process according to claim 2, in which the light fraction, termed the cold condensate and the heavy fraction, termed the waxes, are re-combined and treated in the same fractionation means.
5. A process according to one of claims 1 to 4, in which said hydrogenation catalyst comprises at least one metal from group VIII of the periodic table of the elements and comprises at least one support based on a refractory oxide.
6. A process according to one of claims 1 to 5, in which the group VIII metal is palladium.
7. A process according to claim 6, in which the hydrogenation of the unsaturated olefinic type compounds from at least a portion of said heavy fraction is carried out at a hydrogen/hydrocarbons volume ratio in the range 15 to 35 Nl/l/h.
8. A process according to one of claims 1 to 7, in which a guard bed is used containing at least one guard bed catalyst upstream of the hydrogenation zone, said guard bed being either integrated into the hydrogenation zone upstream of the hydrogenation catalyst bed or placed in a separate zone upstream of the hydrogenation zone.
9. A process according to one of claims 1 to 8, in which said hydroisomerization/hydrocracking step c) is carried out at a pressure in the range 0.2 to 15 MPa, at a space velocity in the range 0.1 h^-1 to 10 h^-1 and a hydrogen ratio in the range 100 to 2000 normal litres of hydrogen per litre of feed per hour and at a temperature in the range 200°C to 450°C.
10. A process according to one of claims 1 to 9, in which said hydroisomerization/hydrocracking catalyst comprises up to 3% by weight of metal of at least one hydro-dehydrogenating element selected from noble metals from group VIII and a support comprising (or preferably consisting of) at least one silica-alumina, said silica-alumina having the following characteristics:

    • a weight content of silica SiO₂ in the range 5% to 95%;

    • a Na content of less than 300 ppm by weight;

    • a total pore volume in the range 0.45 to 1.2 ml/g, measured by mercury porosimetry;

    • the porosity of said silica-alumina being as follows:

    i) the volume of mesopores with a diameter in the range 40 Å to 150 Å and with a mean diameter in the range 80 to 140 Å represents 20-80% of the total pore volume measured by mercury porosimetry;

    ii) the volume of macropores with a diameter of more than 500 Å, preferably in the range 1000 Å to 10000 Å, represents 20% to 80% of the total pore volume, by mercury porosimetry;

    • a specific surface area in the range 100 to 550 m²/g.
11. A process according to one of claims 1 to 9, in which said hydroisomerization/hydrocracking catalyst comprises up to 3% by weight of metal of at least one hydro-dehydrogenating element selected from noble metals from group VIII of the periodic table of the elements, 0.01% to 5.5% by weight of oxide of a doping element selected from phosphorus, boron and silicon, and a non-zeolitic support based on silica-alumina containing a quantity of more than 15% by weight and 95% or less by weight of silica (SiO₂), said silica-alumina having the following characteristics:

    • a mean pore diameter, measured by mercury porosimetry, in the range 20 to 140 Å;

    • a total pore volume, measured by mercury porosimetry, in the range 0.1 ml/g to 0.5 ml/g;

    • a total pore volume, measured by nitrogen porosimetry, in the range 0.1 ml/g to 0.6 ml/g;

    • a BET specific surface area in the range 100 to 550 m²/g;

    • a pore volume, measured by mercury porosimetry, included in pores with a diameter of more than 140 Å, of less than 0.1 ml/g;

    • a pore volume, measured by mercury porosimetry, included in pores with a diameter of more than 160 Å, of less than 0.1 ml/g;

    • a pore volume, measured by mercury porosimetry, included in pores with a diameter of more than 200 Å, of less than 0.1 ml/g;

    • a pore volume, measured by mercury porosimetry, included in pores with a diameter of more than 500 Å, of less than 0.1 ml/g;

    • an X ray diffraction diagram which contains at least the principal characteristic peaks of at least one of the transition aluminas included in the group composed of alpha, rho, chi, eta, gamma, kappa, theta and delta aluminas;

    • a settled catalyst packing density of more than 0.55 g/cm³.
12. A process according to one of claims 1 to 9, in which said hydroisomerization/hydrocracking catalyst comprises between 2.5% and 5% by weight of oxide of an element from group VIII and between 20% and 35% by weight of oxide of a group VIB element with respect to the weight of the final catalyst, optionally 0.01% to 5.5% by weight of oxide of a doping element selected from phosphorus, boron and a non-zeolitic support based on silica-alumina containing a quantity of more than 15% by weight and 95% by weight or less of silica (SiO₂), said silica-alumina having the following characteristics:

    • a mean pore diameter, measured by mercury porosimetry, in the range 20 to 140 Å;

    • a total pore volume, measured by mercury porosimetry, in the range 0.1 ml/g to 0.5 ml/g;

    • a total pore volume, measured by nitrogen porosimetry, in the range 0.1 ml/g to 0.6 ml/g;

    • a BET specific surface area in the range 100 to 550 m²/g;

    • a pore volume, measured by mercury porosimetry, included in pores with a diameter of more than 140 Å, of less than 0.1 ml/g;

    • a pore volume, measured by mercury porosimetry, included in pores with a diameter of more than 160 Å, of less than 0.1 ml/g;

    • a pore volume, measured by mercury porosimetry, included in pores with a diameter of more than 200 Å, of less than 0.1 ml/g;

    • a pore volume, measured by mercury porosimetry, included in pores with a diameter of more than 500 Å, of less than 0.1 ml/g;

    • an X ray diffraction diagram which contains at least the principal characteristic peaks of at least one of the transition aluminas included in the group composed of alpha, rho, chi, eta, gamma, kappa, theta and delta aluminas;

    • a settled catalyst packing density of more than 0.55 g/cm³.
13. A process according to claim 12, in which said catalyst is sulphurized.
14. A process according to one of claims 1 to 13, in which at least a portion of at least one of the kerosene and gas oil cuts from step d) is recycled to step c).

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