RU2592688C2 - Method of converting hydrocarbon material containing shale oil by hydroconversion in fluidised bed, fractionation using atmospheric distillation and hydrocracking - Google Patents

Abstract

FIELD: technological processes.

SUBSTANCE: invention relates to a method of converting shale oil or a mixture of shale oil with nitrogen content at least 0.1 wt%, comprising following steps: a) raw material is introduced in part for hydroconversion in presence of hydrogen, wherein said part comprises at least a reactor with fluidised bed, which operates in mode of gaseous and liquid flow and comprises at least one hydroconversion catalyst on a substrate, b) output stream obtained at step a) is at least partially in fractionation zone, from which, by means of atmospheric distillation are output gaseous fraction, naphtha fraction, gas oil fraction and a fraction heavier than gas oil, c) said naphtha fraction is processed at least partially in first part for hydrotreatment in presence of hydrogen, wherein said part comprises at least one reactor with fixed layer, containing at least one catalyst for hydrotreatment, d) said gas oil fraction is processed at least partially in second part for hydrotreatment in presence of hydrogen, wherein said part comprises at least one reactor with fixed layer, containing at least one catalyst for hydrotreatment, e) fraction heavier than gas oil fraction is processed at least partially in part for hydrocracking in presence of hydrogen. Invention also relates to shale oil processing using said method.

EFFECT: invention provides maximisation of output fuel base.

28 cl, 2 dwg, 2 tbl, 1 ex

Description

The present invention relates to a method for converting shale oil-containing hydrocarbons into lighter products that can be used as fuel and / or petrochemical feedstocks. More specifically, the present invention relates to a method for converting a hydrocarbon feedstock containing shale oil, which comprises a fluidized bed hydroconversion feedstock step, followed by atmospheric distillation fractionation step to obtain a light fraction, a ligroin fraction and a gas oil fraction, and to obtain a heavier fraction, than the gas oil fraction, and the hydrocracking fraction, heavier than the gas oil fraction. This method makes it possible to convert shale oils into a very high quality fuel base and, more specifically, has an excellent yield.

Due to the high volatility of prices per barrel and reduced detection of conventional areas of oil products, oil companies are turning to non-standard sources. Following oil and gas sands and deep-sea areas, oil shales, although relatively poorly known, are becoming increasingly desirable.

Oil shales are sedimentary rocks that contain an insoluble organic matter called kerogen. At a high temperature in situ or ex situ (“distillation in retort”) in the absence of air, at temperatures from 400 to 500 ° C, these shales give off oil, shale oil, a general form similar to crude oil.

Despite its composition other than crude oil, shale oils can be a substitute for the latter, as well as a source of chemical intermediates.

Shale oils cannot be directly used in place of crude oil. In fact, although these oils are similar to oil in some respects (e.g., similar to the H / C ratio), they differ in chemical nature and a much higher level of metallic and / or non-metallic impurities, thus making the conversion of this non-standard source much more complex than oil. Shale oils have, in particular, oxygen and nitrogen levels that are much higher than in oil. They may also contain higher concentrations of olefins, sulfur, or metal compounds (especially compounds containing arsenic).

Shale oils obtained by pyrolysis of kerogen contain a large number of olefin compounds obtained as a result of cracking, and this leads to the need for additional hydrogen at the stage of purification. For example, the bromine index, which makes it possible to calculate the concentration by weight of olefinic hydrocarbons (by adding bromine to the ethylene double bond), is usually greater than 30 g / 100 g of hydrocarbon feed for shale oils, while it is from 1 to 5 g / 100 g of hydrocarbon feed for oil residues. The olefin compounds resulting from cracking essentially consist of monoolefins and diolefins. The unsaturations present in olefins are a potential source of instability during polymerization and / or oxidation.

The oxygen content, as a rule, is higher than in heavy oil, and can be almost 8 wt.% From raw materials. Oxygen compounds are often phenols and carboxylic acids. Therefore, shale oils can have a noticeable acidity.

The sulfur content varies from 0.1 wt.% To 6.5 wt.%, Making strong desulfurization treatments necessary to meet the specifications for the fuel base. Sulfur compounds are in the form of thiophenes, sulfides or disulfides. Moreover, the sulfur distribution profile in shale oil may differ from that obtained in conventional oil.

The most distinctive feature of shale oils, however, is the higher nitrogen content, which makes them unsuitable as conventional raw materials for a refinery. Oil typically contains about 0.2 wt.% Nitrogen, while crude shale oils contain, as a rule, about 1 wt.% To about 3 wt.% Or more nitrogen. Moreover, nitrogen compounds present in oil are generally concentrated in relatively higher boiling ranges, while nitrogen compounds present in crude shale oils are generally distributed over all boiling ranges of the material. Nitrogen compounds in oil are mainly minor compounds, while, in general, about half of the nitrogen compounds present in crude shale oils are basic. These basic nitrogen compounds are particularly undesirable in petroleum refining feeds, as these substances often act as catalyst poisoning agents. In addition, product stability is a problem that is common to many products derived from shale oil. Such instability, including photosensitivity, as it turned out, is essentially the result of the presence of nitrogen compounds. Consequently, crude shale oils should typically undergo a strong refining treatment (high total pressure) in order to obtain synthetic crude oil or fuel base products that meet the current conditions.

It is also known that shale oils can contain many traces of metal compounds, generally present in the form of organometallic complexes. Metal compounds include common pollutants such as nickel, vanadium, calcium, sodium, lead or iron, as well as arsenic metal compounds. In fact, shale oils may contain more than 20 ppm of arsenic, while the amount of arsenic in crude oil typically lies in the ppm range (ppm). All of these metal compounds are catalyst poisoners. More specifically, they irreversibly poison hydroprocessing catalysts and hydrogenation catalysts by uniform deposition on the active surface. Conventional metal compounds and part of arsenic are found mainly in heavy fractions and are removed by precipitation on the catalyst. On the other hand, when products containing arsenic are capable of creating volatile compounds, these compounds can be partially found in lighter fractions and, as a result, can poison the catalysts in subsequent conversion processes, during refining, or in petrochemicals.

In addition, shale oils typically contain sandy sediments originating from areas of tar shale, from which shale oils are extracted. These sand deposits can cause clogging problems, especially in fixed bed reactors.

Finally, shale oils may contain waxes that make their pour point higher than the ambient temperature, thus preventing them from moving in the pipeline.

In view of the significant resources and in view of their evaluation as a promising source of oil, there is a true need for turning shale oils into light products that can be used as fuel and / or raw materials for petrochemicals. Methods for the conversion of shale oils are known. Conversion is usually carried out in practice, alternatively by coking, hydrocracking (thermal cracking in the presence of hydrogen) or by hydroconversion (catalytic hydrogenation). Liquid / liquid extraction processes are also known.

Thus, patent document FR 2197968 describes a method for filtering and hydrogenating shale oils or tar sand oils containing particles, comprising steps comprising (a) continuously introducing said oil at the bottom of the reactor with a mixture of hydrogen, (b) periodically introducing the catalyst at the top the reactor and removing the catalyst, and trapping particles at the bottom of the reactor to allow the catalyst to pass through the reactor, (c) measuring the pressure drop between the bottom of the reactor and the top of the reactor, and (d) setting the catalyst flow rate d To adjust the pressure drop to a pre-selected pressure that matches the desired filtration rate in the reactor. The method described in FR 2197968, in particular, does not contain the use of independent parts for hydroprocessing fractions of naphtha and gas oil.

US Pat. No. 6,153,087 describes a process for converting heavy feedstocks comprising fluidized bed conversion and a hydrocracking operation. This method is applied to various heavy feedstocks having an initial boiling point of at least 300 ° C. Application to shale oils is not mentioned and not intended. The use of independent parts for the hydrotreatment of ligroin and gas oil fractions was not considered.

Object of the invention

The specific feature of shale oils, consisting of a certain number of metallic and / or non-metallic impurities, makes the conversion of this non-standard source much more difficult than oil. The industrial development of methods for converting shale oils therefore needs to develop methods that are suitable for raw materials that maximize the output of a high quality fuel base. Conventional cleansing treatments known to oil should be adapted to the specific composition of shale oils.

The present invention contributes to the improvement of known methods for the conversion of hydrocarbon materials containing shale oil by increasing, in particular, the yield of the fuel base for a combination of steps having a specific bond and processing corresponding to each fraction obtained from shale oils. Similarly, it is an object of the present invention to provide high quality products having, more specifically, a low content of sulfur, nitrogen and arsenic, preferably as described. Another objective is to provide a method that is simple, that is, it has as few stages as necessary, while remaining efficient, allowing you to limit the cost of investment.

In its broadest form and according to a first aspect, the present invention relates to a method for converting hydrocarbon feedstocks containing at least one shale oil having a nitrogen content of at least 0.1%, often at least 1% and very often at least 2 wt.% , characterized in that it contains the following stages:

a) the feed is introduced into the hydroconversion section in the presence of hydrogen, said portion comprising at least a fluidized bed reactor operating in a gaseous and liquid ascending mode and containing at least one hydroconversion catalyst on a support,

b) the effluent obtained in stage a) is introduced, at least partially and often completely, into the fractionation zone, from which, through atmospheric distillation, a gaseous fraction, a ligroin fraction, a gas oil fraction and a heavier fraction than the gas oil fraction exit ,

c) said ligroin fraction is treated, at least partially and often completely, in a first hydrotreatment part in the presence of hydrogen, said part comprising at least one fixed bed reactor containing at least one hydrotreatment catalyst,

d) said gas oil fraction is treated, at least partially and often completely, in a second hydrotreatment part in the presence of hydrogen, said part comprising at least one fixed-bed reactor containing at least one hydrotreatment catalyst,

e) a fraction heavier than the gas oil fraction is processed, at least partially and often completely, in the hydrocracking portion in the presence of hydrogen.

The hydroconversion part in step a) typically contains one to three, and preferably two, reactors in series, and the first and second parts for hydroconversion in steps c) and d) independently contain one to three reactors in series.

The research work carried out by the authors on the conversion of shale oils led to the discovery that the improvement of existing methods, in terms of the output of the fuel base and in terms of product purity, is possible by combining various stages connected in a special way. Each fraction obtained by the method according to the present invention is sequentially introduced into the processing part.

First, hydrocarbon feeds containing shale oil undergo fluidized bed hydroconversion. The fluidized bed technique, relative to the fixed bed technique, facilitates the processing of raw materials that are heavily contaminated with metals, heteroatoms and sediments, such as shale oils, while exhibiting a conversion rate that is typically greater than 50%. In fact, in this first stage, shale oil turns into molecules that are capable of creating a fuel base in the future. Most metal compounds, residues and heterocyclic compounds are removed. The stream leaving the fluidized bed thus contains most of the stable nitrogen and sulfur compounds, and possibly the volatile arsenic compounds that are present in the lighter components.

The effluent obtained in the hydroconversion stage is then fractionated by atmospheric distillation, creating various fractions for which a treatment specific to each fraction is successively carried out. Atmospheric distillation facilitates the production, at the first stage, of various desired fractions (naphtha, gas oil), thus facilitating the downstream hydrotreatment adapted for each fraction and, therefore, the direct production of gas oil or naphtha fuel base products that satisfy different technical conditions. Therefore, fractionation after hydroprocessing is not necessary.

Due to the high level of reduction of pollution in the fluidized bed, light fractions (naphtha and gas oil) contain less pollutants and can therefore be processed in parts with a fixed layer, which, as a rule, has improved hydrogenation kinetics compared to the fluidized bed. Similarly, operating conditions can be mild due to the limited pollutant content. Processing for each fraction allows better performance with respect to the desired products. Depending on the selected operating conditions (more or less stringent), it is possible to obtain either a fraction that can be introduced into the fuel pool, or a final product that meets the current technical specifications (sulfur content, maximum height of non-smoking flame, cetane, aromatic components, etc. .d.).

Upstream of the hydroprocessing catalyst bed, the fixed-bed hydroprocessing portions preferably contain specific protective layers for any arsenic compounds or silicon compounds contained within the diesel engine and / or naphtha. Arsenic compounds released from the fluidized bed (because they are usually relatively volatile) are captured by the protective layers, thus preventing the poisoning of downstream catalysts and contributing to the production of a very arsenic depleted fuel base.

Atmospheric distillation also contributes to the concentration of most stable nitrogen compounds in a fraction that is heavier than gas oil and which undergoes hydrocracking during step e). This hydrocracking stage provides an improvement in the quality of the fraction heavier than gas oil in the production of lighter products and, therefore, minimizes the problems of utilization and economic yields of this fraction.

DETAILED DESCRIPTION OF THE INVENTION

Hydrocarbon feed

The hydrocarbon feed contains at least one shale oil or a mixture of shale oils. The term "shale oil" is used in this application in its broadest sense and is intended to include any shale oil or a fraction of shale oil that contains nitrogen impurities. It includes crude shale oil, obtained either by pyrolysis, by extraction with a solvent, or other means, or shale oil that has been filtered to remove solids, or which has been treated with one or more solvents, chemicals or other treatments, and which contains nitrogen impurities. The term “shale oil” also contains shale oil fractions obtained by distillation or another fractionation technique.

The shale oils used according to the present invention typically have a Conradson carbon residue of at least 0.1 wt.% And, as a rule, at least 5 wt.%, An asphaltene content (IP143 standard / s C7) of at least 1 %, often at least 2 wt.%. The sulfur content in them, as a rule, is at least 0.1%, often at least 1% and very often at least 2%, and even up to 4% or even 7 wt.%. The amount of metals that they contain is typically at least 5 parts per million, often at least 50 parts per million, and typically at least 100 parts per million, or at least 200 parts by weight per million. The nitrogen content in them, as a rule, is at least 0.5%, often at least 1% and very often at least 2 wt.%. The arsenic content in them, as a rule, is more than 1 mass parts per million and up to 50 mass parts per million.

The method according to the present invention is intended for the conversion of shale oils. However, the feed may optionally contain, in addition to shale oil, other synthetic liquid hydrocarbons, more particularly those containing a substantial amount of cyclic organic nitrogen compounds. These include oils derived from coal, oils based on heavy resins, tar sands, pyrolytic oils from wood residues such as wood residues, crude oil derived from biomass (“bio-raw materials”), vegetable oils and animal fats.

Other hydrocarbon feedstocks may also provide shale oil or a mixture of shale oils. The feed is selected from the group consisting of vacuum distillates and direct distillation residues, vacuum distillates and non-converted residues obtained during conversion processes, such as, for example, obtained during distillation to a coke point (coking), products obtained from the hydroconversion of heavy fractions fixed bed products derived from the hydroconversion of heavy fractions with a fluidized bed and oils deasphalted using solvents (for example, oils deasphalted with propane, butane and ne Thane occurring during the process the deasphalting of vacuum residues of direct distillation or vacuum residues obtained from the hydroconversion processes). The feed may further comprise light cyclic oil (LCO) of various origins, heavy cyclic oil (HCO) of various origins, and gas oil fractions that originate from catalytic cracking and typically have a distillation range of from about 150 ° C to about 650 ° C . The feed may also contain aromatic extracts obtained from the production of lubricating oils. Raw materials can also be obtained and used in mixtures, in any proportions.

Hydrocarbons added to shale oil or to a mixture of shale oils can comprise from 20% to 60% by weight of all raw materials (shale oil or a mixture of shale oils + added hydrocarbons), or from 10% to 90% by weight.

Hydroconversion

Raw materials containing shale oil are primarily subjected to a fluidized bed hydroconversion step [step a)]. Hydroconversion is understood as hydrogenation, hydrotreatment, hydrodesulfurization, hydrodenitrogenation, hydrodemetallization and hydrocracking reactions.

The operation of a fluidized bed catalytic reactor, including the recycling of liquids from the reactor to the top through a stirred catalytic bed, is well known. Fluidized bed techniques employ catalysts on a substrate, typically in the form of extrudates having a diameter of typically about 1 mm or less than 1 mm, for example greater than or equal to 0.7 mm. Catalysts remain inside reactors and are not removed with products. The catalytic activity may remain constant due to the continuous substitution (addition and withdrawal) of the catalyst. Therefore, there is a need to shut down the assembly in order to replace the used catalyst, or to increase the reaction temperature during the cycle to compensate for deactivation. Moreover, working with constant working conditions makes it possible to coordinate product quality and yields obtained per catalyst cycle. Since the catalyst is kept in a state of mixing through substantial liquid recycling, the pressure loss across the reactor remains low and constant, and the heat of reaction is quickly averaged over the catalyst bed, which is therefore almost isothermal and does not require cooling by injection of quenchers. The fluidized bed hydroconversion avoids the problems of catalyst contamination associated with the deposition of impurities naturally present in shale oils.

The conditions in step a) of processing the feed in the presence of hydrogen are standard fluidized bed hydroconversion conditions for a liquid hydrocarbon fraction. They usually operate at a total pressure of from 2 to 35 MPa, preferably from 10 to 20 MPa, at a temperature of from 300 ° C to 550 ° C and often from 400 ° C to 450 ° C. The hourly average feed rate (HSV) and the partial pressure of hydrogen are important factors that are selected according to the characteristics of the product to be processed and the desired conversion. HSV, as a rule, lies in the range from 0.2 h ^-1 to 1.5 h ^-1 and preferably from 0.4 h ^-1 to 1 h ^-1 . The amount of hydrogen mixed with the feed is typically from 50 to 5000 normal cubic meters (Nm ³ ) per cubic meter (m ³ ) of liquid feed, and typically from 100 to 1000 Nm ³ / m ³ , and preferably from 300 to 500 Nm ³ / m ³ .

This hydroconversion step a) can typically be carried out under the conditions of the T-STAR® process, as described, for example, in Heavy Oil Hydroprocessing published by AlChE, March 19-23, 1995, Houston, Texas, paper number 42d. It can also be carried out under the conditions of the H-OIL® process, as described, for example, in an article published by NPRA, Annual Meeting, March 16-18, 1997, J.J. Colyar and L.I. Wisdom called The H-Oil® Process, A Worldwide Leader In Vacuum Residue Hydroprocessing.

Hydrogen necessary for hydroconversion (and subsequent hydrotreatment operations) can come from steam reforming of hydrocarbons (methane) or from gas obtained from shale oils during the production of shale oils.

The catalyst in step a) is preferably a conventional granular hydroconversion catalyst containing, on an amorphous support, at least one metal or metal compound having (having) a hydrodehydrogenation function. Generally speaking, the catalyst is used whose pore distribution is suitable for processing raw materials containing metals.

The hydrodehydrogenation function may be provided by at least one group VIII metal selected from the group consisting of nickel and / or cobalt, optionally in combination with at least one group VIB metal selected from the group consisting of molybdenum and / or tungsten . It is possible, for example, to use a catalyst containing from 0.5% to 10 wt.% Nickel and preferably from 1% to 5 wt.% Nickel (in the form of nickel oxide, NiO) and from 1% to 30 wt.% Molybdenum, preferably from 5 % to 20 wt.% molybdenum (in the form of molybdenum oxide, MoO ₃ ), on an amorphous inorganic substrate. The total amount of metal oxides of groups VIB and VIII is often from 5% to 40 wt.% And in general from 7% to 30 wt.%. The mass ratio, expressed as a Group VI metal oxide (or metals) to a Group VIII metal oxide (or metals), is typically from about 20 to about 1 and, as a rule, from about 10 to about 2.

The catalyst support will be selected, for example, from the group consisting of alumina, silica, aluminosilicates, magnesium oxide, clays and mixtures of at least two of these minerals. This substrate may also include other compounds, for example, oxides selected from the group consisting of boron oxide, zirconium oxide, titanium oxide and phosphoric anhydride. Typically, an alumina support is used and very often an alumina support doped with phosphorus and, if necessary, boron. In this case, the concentration of phosphoric anhydride, P ₂ O ₅ , is usually less than about 20 wt.% And usually less than about 10 wt.%, And at least 0.001 wt.%. The concentration of boron trioxide, B ₂ O ₃ , as a rule, is from about 0% to about 10 wt.%. The alumina used is typically γ (gamma) or η (this) alumina. This catalyst is typically used in the form of an extrudate. The catalyst in step a) is preferably based on nickel and phosphorus doped molybdenum and on an alumina support. An HTS 458 catalyst sold by Axens may be used, for example.

Before introducing the raw materials, the catalysts used in the method according to the present invention can be subjected to sulfurization treatment, with the conversion, at least in part, of the metal groups to sulfides, before they come into contact with the raw material to be treated. This activating treatment by sulfurization is well known to specialists in this field of technology and can be carried out by a method already described in the literature, either in situ, i.e. inside the reactor, or ex situ.

The spent catalyst is often replaced with a fresh catalyst by withdrawing from the bottom of the reactor and introducing fresh or new catalyst at the top of the reactor, at regular intervals, for example by conventional or quasi-continuous addition. It is possible, for example, to introduce a fresh catalyst every day. The replacement level of the spent catalyst with a fresh catalyst can be, for example, from about 0.05 kg to about 10 kg per m ^{3 of} feedstock. This conclusion and this substitution are carried out using devices that provide continuous operation of this stage of hydroconversion. The assembly typically comprises a recirculation pump to maintain the fluidized bed catalyst by continuously recirculating at least a portion of the liquid removed from the top of the reactor and re-entering it at the bottom of the reactor. It is also possible to transport spent catalyst discharged from the reactor to a regeneration zone in which the carbon and sulfur that it contains are removed, and then return this regenerated catalyst to the hydroconversion step a).

Operating conditions associated with catalytic activity provide possible degrees of conversion of the feed from 50% to 95%, preferably from 70% to 95%. The above conversion is defined as the mass fraction of the feed at the beginning of the reaction minus the mass fraction, the heavy fraction having a boiling point of more than 343 ° C, at the end of the reaction, this value being divided by the mass fraction of the feed at the beginning of the reaction.

The fluidized bed technique allows the processing of raw materials that are heavily contaminated with metals, precipitates and heteroatoms, without the problems of pressure loss or clogging problems that are known when using a fixed layer. Metals, such as nickel, vanadium, iron and arsenic, are largely removed from the feed by precipitation on the catalysts during the reaction. Removable (volatile) arsenic will be removed at the hydrotreatment stages using specific protective layers. Sediments present in shale oils are also removed by replacing the catalyst in a fluidized bed without disrupting hydroconversion reactions. These stages also ensure the removal, hydrodenitrogenation of the main part of nitrogen, leaving only the majority of stable nitrogen compounds.

The hydroconversion stage a) makes it possible to obtain an effluent having a nitrogen content that is significantly reduced relative to the nitrogen content of the feed, about 3 times to 10 times lower than the nitrogen content of the feed.

Atmospheric distillation fractionation

The effluent obtained from the hydroconversion step a) is introduced at least partially, and preferably completely, into the fractionation zone from which the gaseous fraction, naphtha, gas oil fraction and a fraction heavier than the gas oil fraction are separated by atmospheric distillation.

The effluent obtained in step a) is preferably fractionated by atmospheric distillation into a gaseous fraction having a boiling point of less than about 50 ° C, a naphtha boiling from about 50 ° C to about 150 ° C, a gas oil fraction boiling from about 150 ° C to about 370 ° C, and a fraction that is heavier than the gas oil fraction, and which typically boils at a temperature above 340 ° C, preferably at a temperature above 370 ° C.

Ligroin and diesel fractions are then separately introduced into the parts for hydroprocessing. A fraction heavier than the ligroin fraction is introduced into the hydrocracking portion in step e).

The gaseous fraction contains gases (H ₂ , H ₂ S, NH ₃ , H ₂ O, CO ₂ , CO, C ₁ -C ₄ hydrocarbons, etc.). It can preferably be purified to recover hydrogen and to recycle it into the hydroconversion part in step a) or the hydrotreatment part in steps c) and d). After purification, C ₃ and C ₄ hydrocarbons can be used to form LPG (liquefied petroleum gas) products. Uncondensed gases (C ₁ -C ₂₎ is generally used as fuel for domestic heating furnaces reactors hydroconversion and / or hydrotreatment and / or hydrocracking.

Hydrocracking

The method according to the present invention comprises a hydrocracking step [step e)], in which at least one part, preferably the entire volume, of a fraction heavier than the gas oil obtained in step b) is sent to the hydrocracking part in the presence of hydrogen, in which the specified fraction, heavier than gas oil, is processed, as a rule, under conditions well known to specialists in this field of technology, to obtain a second gaseous fraction, a second fraction of naphtha, a second gas oil fraction and a second fraction, heavier loi than gasoline, referred to as "the unconverted oil." The second fraction of naphtha will, for example, be processed, at least partially and often completely, in part for hydrotreatment in step c). The second gas oil fraction, for example, at least partially and often completely, will be hydrotreated in step d). The second fraction, heavier than gas oil, for example, at least partially or even completely, will be sent to the pool for heavy fuel oil and / or recycled, at least partially or even completely, to the hydrocracking step e) and / or to the stage hydroconversion a).

Hydrocracking effluents obtained at the end of step e) can also be separated into a gas oil fraction and a fraction lighter than the gas oil fraction and a second fraction heavier than the gas oil. This gas oil fraction and a lighter fraction than gas oil are a mixture of a second gaseous fraction, a second naphtha fraction and a second naphtha fraction.

The gas oil and a fraction lighter than gas oil can be directed, at least partially and often completely, to the fractionation zone in step b).

A brief description of hydrocracking can be found, for example, in ULLMANS ENCYCLOPEDIA OF INDUSTRIAL CHEMISTRY, VOLUME A18, 1991, page 71. Typically, a conventional catalyst or a set of conventional catalysts located on different fixed layers is used. The catalysts used contain combinations of metals on a substrate of aluminum oxides or zeolites. Examples of catalysts used in the context of industrial applications of hydrocracking are Ni-Mo catalysts on alumina, Ni-Mo catalysts on zeolite, Ni-Mo and Ni-W catalysts on aluminosilicate, Co-Mo catalysts on alumina and Co-Mo catalyst on zeolite. These catalysts may contain, as a function of the desired properties, other metals selected from transition metals and rare earth metals, in trace amounts or in relatively larger proportions (from less than 1 wt.% To 30 wt.% Relative to the total loading of metals) in metal form or in oxide form.

Hydrocracking is carried out in a vertical reactor, usually in a downward flow mode. The feed is preheated in the presence of hydrogen before being introduced at the top of the reactor. A hydrogen composition is introduced between each catalyst bed (quenching gas) to reduce temperature. This quenching gas mixes strongly with the feedstock, typically in devices known as “blowing boxes”.

The choice of catalyst and operating conditions depends on the desired products, as a function of the processed feed. Hydrocracking units, as a rule, operate at temperatures from 320 ° C to 450 ° C, preferably from 350 ° C to 400 ° C, with mass hourly consumption from 0.3 to 7 h ^-1 , with a hydrogen / feed ratio of from 300 to 1000 Nm ³ hydrogen / m ³ raw materials. Two types of hydrocracking units are distinguished, depending on their working pressure: (1) MHC or soft hydrocracking units, which operate, as a rule, at a pressure of 8 to 15 MPa, more often 10 to 12 MPa, and (2) DHC or nodes for hydrocracking distillates, which operate, as a rule, at a pressure of from 12 to 20 MPa, more often from 15 to 20 MPa.

The hydrocracking step of a fraction heavier than gas oil e) is carried out at a temperature of from 350 ° C to 450 ° C, preferably from 370 ° C to 425 ° C, at a total pressure of 10 to 20 MPa, preferably from 15 to 18 MPa, with a mass hourly flow rate ((feed time / hour) / catalyst time) of 0.3 to 7 h ^-1 , preferably 0.5 h ^-1 to 1.5 h ^-1 , and with a hydrogen / feed ratio of 100 to 5000 Nm ³ / m ³ , preferably from 1000 to 2000 Nm ³ / m ³ .

The use of the MHC unit, in the context of the present invention, provides effluents that are converted by about 10-20%, which is sufficient to form a synthetic crude oil after mixing with various fractions of naphtha and gas oil obtained during the process. This synthetic crude product can then be sent to a conventional refining step. Alternatively, the use of a DHC assembly, in the context of the present invention, provides effluents that are 80-90% converted, which should make it possible to use products for industrial applications as a base for fuel production.

Hydrotreating ligroin and gas oil fractions

The ligroin and gas oil fractions are then separately hydrotreated with a fixed bed [steps c) and d)]. Hydrotreating refers to hydrodesulfurization, hydrodenitrogenation and hydrodemetallization reactions. The task, depending on the working conditions, which are chosen more or less strict, is to obtain various fractions according to the technical conditions (sulfur content, maximum height of non-smoking flame, cetane, content of aromatic substances, etc.) or to obtain synthetic crude oil . Processing ligroin in one part for hydroprocessing and a fraction of gas oil in another part for hydroprocessing provides improved performance in terms of operating conditions, so as to ensure that each fraction meets the required technical conditions with a maximum output and in one stage per fraction. Thus, fractionation after hydroprocessing is not necessary. The difference between the two parts for hydroprocessing is more based on differences in operating conditions than on the choice of catalyst.

The fixed-bed hydroprocessing portions preferably comprise upstream specific catalyst layers for the arsenic compounds (arsenic containing compounds) and silicon compounds that are optionally present in naphtha and / or diesel fractions. Compounds containing arsenic released from the fluidized bed (being, as a rule, relatively volatile) are captured by the protective layers, thus preventing the poisoning of catalysts located downstream and making it possible to obtain a fuel base that is very depleted in arsenic.

Protective layers that remove arsenic and silicon from fractions of naphtha or gas oil are well known to those skilled in the art. They contain, for example, an absorbent material containing nickel deposited on an appropriate substrate (silica, magnesium oxide or alumina), as described in FR 2617497, or else an absorbent material containing copper on a substrate, as described in FR 2762004. mention protective layers supplied by Axens: ACT 979, ACT 989, ACT 961, ACT 981.

The operating conditions in each hydroprocessing unit are adapted for the raw material to be processed. The operating conditions for hydrotreatment of naphtha are generally milder than the operating conditions for hydrotreating a gas oil fraction.

At the hydrotreatment stage, ligroin [stage c)] is usually operated at an absolute pressure of 4 to 15 MPa, often 10 to 13 MPa. The temperature during this step c) is usually from 280 ° C to 380 ° C, often from 300 ° C to 350 ° C. This temperature is usually set in accordance with the desired level of hydrodesulfurization. The hourly average feed rate (HSV) is typically in the range from 0.1 h ^-1 to 5 h ^-1 , and preferably from 0.5 h ^-1 to 1 h ^-1 . The amount of hydrogen mixed with the feed is typically from 100 to 5000 normal cubic meters (Nm ³ ) per cubic meter (m ³ ) of liquid feed, and typically from 200 to 1000 Nm ³ / m ³ , and preferably from 300 to 500 Nm ³ / m ³ . It is useful to work in the presence of hydrogen sulfide (for sulfurization of the catalyst), and the partial pressure of hydrogen sulfide is usually from 0.002 times to 0.1 times, and preferably from 0.005 times to 0.05 times the total pressure.

At the hydroprocessing stage, gas oil fractions [stage d)] usually operate at an absolute pressure of from 7 to 20 MPa, often from 10 to 15 MPa. The temperature during this step d) is usually from 320 ° C to 450 ° C, often from 340 ° C to 400 ° C. This temperature is usually set in accordance with the desired level of hydrodesulfurization. Mass hourly consumption ((feed time / hour) / catalyst time) is from 0.1 to 1 h ^-1 . The hourly average feed rate (HSV) is typically in the range from 0.2 h ^-1 to 1 h ^-1 and preferably from 0.3 h ^-1 to 0.8 h ^-1 . The amount of hydrogen mixed with the feed is typically from 100 to 5000 normal cubic meters (Nm ³ ) per cubic meter (m ³ ) of liquid feed, and typically from 200 to 1000 Nm ³ / m ³ , and preferably from 300 to 500 Nm ³ / m ³ . It is useful to work in the presence of hydrogen sulfide (for sulfurization of the catalyst), and the partial pressure of hydrogen sulfide is usually from 0.002 times to 0.1 times, and preferably from 0.005 times to 0.05 times the total pressure.

In parts for hydroprocessing, an ideal catalyst should have a high hydrogenating ability so as to produce thoroughly refined products and achieve a significant reduction in sulfur and nitrogen. In a preferred embodiment of the present invention, the hydroprocessing parts operate at a relatively low temperature, which facilitates careful hydrogenation and limits coking of the catalyst. The use of one catalyst or two or more different catalysts, simultaneously or sequentially, in parts for hydroprocessing will not go beyond the scope of the present invention. The hydroprocessing in steps c) and d) is usually carried out industrially in one or more liquid downstream reactors.

In two parts, the same type of catalyst is used for the hydrotreatment [steps c) and d)]; the catalysts in each part may be the same or different. At least one fixed bed of a conventional hydrotreating catalyst is used, comprising, on an amorphous substrate, at least one metal or metal compound having a hydrodehydrogenation function.

The hydrodehydrogenation function may be provided by at least one group VIII metal selected from the group consisting of nickel and / or cobalt, optionally in combination with at least one group VIB metal selected from the group consisting of molybdenum and / or tungsten . It is possible, for example, to use a catalyst containing from 0.5% to 10 wt.% Nickel and preferably from 1% to 5 wt.% Nickel (in the form of nickel oxide, NiO) and from 1% to 30 wt.% Molybdenum, preferably from 5 % to 20 wt.% molybdenum (in the form of molybdenum oxide, MoO ₃ ), on an amorphous inorganic substrate. The total amount of metal oxides of groups VIB and VIII is often from 5% to 40 wt.% And in general from 7% to 30 wt.%. The mass ratio, expressed as a Group VI metal oxide (or metals) to a Group VIII metal oxide (or metals), is typically from about 20 to about 1 and, as a rule, from about 10 to about 2.

The catalyst support will be selected, for example, from the group consisting of alumina, silica, aluminosilicates, magnesium oxide, clays and mixtures of at least two of these minerals. This substrate may also include other compounds, for example, oxides selected from the group consisting of boron oxide, zirconium oxide, titanium oxide and phosphoric anhydride. Typically, an alumina support is used and very often an alumina support doped with phosphorus and, if necessary, boron. In this case, the concentration of phosphoric anhydride, P ₂ O ₅ , is usually less than about 20 wt.% And usually less than about 10 wt.%, And at least 0.001 wt.%. The concentration of boron trioxide, B ₂ O ₃ , as a rule, is from about 0% to about 10 wt.%. The alumina used is typically γ (gamma) or η (this) alumina. This catalyst is typically used in the form of extrudates.

Prior to introducing the feed, the catalysts used in the process of the present invention may be subjected to a sulfurization treatment to convert, at least in part, the metal groups to sulfides before they come into contact with the feed to be treated. This activating treatment by sulfurization is well known to specialists in this field of technology and can be carried out by a method already described in the literature, either in situ, i.e. inside the reactor, or ex situ.

The hydrotreatment in step c) of the ligroin fraction results in a fraction containing not more than 1 mass parts per million nitrogen, preferably not more than 0.5 mass parts per million nitrogen, and not more than 5 mass parts per million sulfur, preferably not more than 0.5 mass parts per million sulfur.

The hydrotreatment in step d) of the gas oil fraction results in a fraction containing not more than 100 parts by mass per million nitrogen, and not more than 20 parts by mass of nitrogen, and not more than 50 parts by mass of sulfur, preferably not more than 10 parts by mass parts per million sulfur.

According to the penultimate object, the present invention relates to the production of synthetic petroleum feedstock by the method according to one of the preceding objects.

According to a last aspect, the present invention relates to a plant for treating shale oil using a method according to one of the preceding objects.

Such an installation contains:

- part for hydroconversion in the presence of hydrogen, containing a fluidized bed reactor operating in a gaseous and liquid upward flow mode and containing at least one hydroconversion catalyst on a substrate,

- fractionation zone through atmospheric distillation,

- the first part for hydroprocessing in the presence of hydrogen, containing a fixed-bed reactor containing at least one hydroprocessing catalyst,

- the second part for hydroprocessing in the presence of hydrogen, containing at least one fixed-bed reactor containing at least one hydroprocessing catalyst,

- part for hydrocracking in the presence of hydrogen.

These elements are arranged to implement the method according to the present invention.

Accordingly, for example:

- the hydroconversion part is connected to the fractionation zone in order to feed this fractionation zone by the effluent from the hydroconversion part,

- the first pipe (line) connects the fractionation zone to the first hydroprocessing part, the second pipe (line) connects the fractionation zone to the second hydroprocessing part.

The installation may further comprise one or more recirculation pipes for introducing various fractions into the hydroconversion removal part, into the hydrocracking part, or into any of the first and second parts for hydrotreatment.

Figure 1 shows in diagrammatic form the method according to the present invention. Figure 2 in the form of a diagram shows a variant of the method in which the separation of several fractions is carried out in the same distillation unit.

According to Fig. 1, a feed containing shale oil (1) to be treated enters through a line (2) into a fluidized bed hydroconversion section (3) in the presence of hydrogen (4), and hydrogen (4) is introduced via line (5) ) The stream leaving the fluidized bed hydroconversion section (3) is introduced via line (6) to the atmospheric distillation column (7), at the end of which there is a gaseous fraction (8), a ligroin fraction (9), a gas oil fraction (10), and fraction (11), heavier than the gas oil fraction. The gaseous fraction (8) as well as the second gaseous fraction (26) containing hydrogen can be purified (not shown) to recycle hydrogen and introduce it (i) into the fluidized bed hydroconversion section (3) along line (2) and / or (5) and / or (ii) in the hydrotreatment part (12) along line (18) and / or (14) and / or (iii) in the hydrotreatment part (13) along line (19) and / or (15) and / or (iv) in the hydrocracking part (20) along line (21) and / or (22). The naphtha fraction (9) is introduced into the fluidized-bed hydrotreatment section (12), at the end of which the naphtha fraction (16) comes out, which is depleted in impurities. The gas oil fraction (10) is introduced into the hydrotreatment section with a fixed layer (13), at the end of which the gas oil fraction (17), depleted in impurities, comes out. Two parts for hydroprocessing (12) and (13) are fed with hydrogen along lines (14) and (15). Fraction (11), heavier than the gas oil fraction, is sent to the hydrocracking part (20) along line (21) to the separation part (25), upon exiting which the second gaseous fraction (26), the second ligroin fraction (27) exit ), the second gas oil fraction (28) and the second fraction, heavier than the gas oil fraction (29). The second fraction of naphtha (27) can be directed, in whole or in part, to the hydrotreatment unit (12) along line (30). The second gas oil fraction (28) is preferably sent to the gas oil pool or can be directed, in whole or in part, to the hydrotreatment part (13) along line (31). The second fraction, which is heavier than the gas oil fraction (29), can (i) be withdrawn and / or (ii) directed back, in whole or in part, to the hydrocracking part (20) along line (32), and / or (iii ) go back, in whole or in part, to the fluidized-bed hydroconversion section (3) along line (33).

In FIG. 2, the hydroconversion, separation and hydroprocessing steps (and reference symbols) are identical to those shown in FIG. 1 prior to the hydrocracking step, which shows some differences.

Raw materials containing shale oil (1) to be processed enter line (2) into the fluidized bed hydroconversion section (3) in the presence of hydrogen (4), and hydrogen (4) is introduced via line (5). The stream leaving the fluidized bed hydroconversion section (3) is introduced via line (6) to the atmospheric distillation column (7), at the end of which a gaseous fraction (8), a naphtha fraction (9), a gas oil fraction (10) and fraction (11), heavier than the gas oil fraction. The gaseous fraction (8) containing hydrogen can be purified (not shown) to recycle hydrogen and introduce it (i) into the fluidized bed hydroconversion section (3) along line (2) and / or (5), and / or (ii) in the part for hydroprocessing (12) along the line (18) and / or (14), and / or (iii) in the part for hydroprocessing (13) along the line (19) and / or (15), and / or (iv) in the hydrocracking portion (20) along line (21) and / or (22). The naphtha fraction (9) is introduced into the hydrotreatment unit with a fixed layer (12), at the end of which the naphtha fraction (16) comes out, depleted in impurities. The gas oil fraction (10) is introduced into the hydrotreatment section with a fixed layer (13), at the end of which the gas oil fraction (17), depleted in impurities, comes out. Two parts for hydroprocessing (12) and (13) are fed with hydrogen along lines (14) and (15). Fraction (11), heavier than the gas oil fraction, is sent to the hydrocracking unit (20) along line (21). Hydrocracking effluents (23) are sent via line (24) to a separation part (34), at the outlet of which, at the top, a mixture (35) containing a second gaseous fraction, a second ligroin fraction and a second gas oil fraction (28) is discharged, and at the bottom, the second fraction is heavier than the gas oil fraction (29). The mixture (35) is sent via line (36) to the distillation column (7). The second fraction, heavier than gas oil (29), can be (i) diverted and / or (ii) directed back, in whole or in part, to the hydrocracking part (20) along line (32), and / or (iii) directed back, in whole or in part, to the fluidized bed hydroconversion section (3) along line (33).

Example

Process shale oil, which has the characteristics shown in Table 1.

Table 1 Characteristics of oil based on shale oil Density 15/4 - 0.945 Hydrogen wt.% 10.9 Sulfur wt.% 1.9 Nitrogen wt.% 0.8 Oxygen wt.% 1.8 Asphaltenes wt.% 1.8 Conradson carbon residue wt.% 3.6 Metals parts per million 236

Shale oil is treated in a fluidized bed reactor containing Axens industrial catalyst HTS458.

The operating conditions are as follows:

- The temperature in the reactor: 435 ° C

- Pressure: 195 bar (19.5 MPa)

- The ratio of hydrogen / raw materials: 600 Nm ³ / m ³

- Total HSV: 0.3 h ^-1

Liquid products obtained from the reactor are fractionated by atmospheric distillation to obtain ligroin (C5 + - 150 ° C), a gas oil fraction (150-370 ° C) and a residual fraction of 370 ° C +, which makes up a fraction heavier than gas oil.

Ligroin is subjected to fixed-bed hydroprocessing using a NiMo alumina catalyst.

The operating conditions are as follows:

- Temperature in the reactor: 320 ° C

- Pressure: 50 bar (5 MPa)

- The ratio of hydrogen / raw materials: 400 Nm ³ / m ³

- Total HSV: 1 h ^-1

The gas oil fraction is subjected to fixed-bed hydroprocessing using a NiMo catalyst on alumina.

The operating conditions are as follows:

- The temperature in the reactor: 350 ° C

- Pressure: 120 bar (12 MPa)

- The ratio of hydrogen / raw materials: 400 Nm ³ / m ³

- Total HSV: 0.6 h ^-1

The heavier fraction than gas oil is then hydrocracked using catalysts containing NiMo on alumina, NiW on aluminosilicate and NiMo on zeolite. This pre-heated feed in the presence of hydrogen is introduced at the top of a vertical reactor containing 5 catalyst beds. The operating pressure is 16 MPa absolute, the temperature is 380 ° C, the hydrogen / feed ratio is 1200 Nm ³ / m ³ , and the HSV is 0.6 h ^-1 . A hydrogen composition is introduced between each catalyst bed (quenching gas) to reduce temperature. This quenching gas mixes strongly with the raw materials in devices known as “blowing boxes”.

Hydrocracked hydrocarbons are diverted to the bottom of the reactor and cooled. They are sent to the fractionation unit, from which at least one naphtha fraction, at least one gas oil fraction and at least one fraction heavier than gas oil are released in the form of superheated gases in the form of bottom residues.

Table 2 summarizes the properties of the various feedstocks at each stage, as well as the yields obtained at various sites, and the total yield. Therefore, it is observed that starting from 100% by weight of shale oil, 93.9% by weight of products (LPG, naphtha, middle distillates) are obtained that meet Euro V specifications.

table 2 Petrochemical plant H-Oil _DC Hydrocracking Raw materials C5 + shale oil Bottom residues ex H-Oil _DC Product Bottom residues ex H-Oil _RC Product yield relative to shale oil based raw materials wt.% 16.0 Product properties Density (d15 / 4) - 0.852 Sulfur wt.% 0.05 Total nitrogen wt.% 0.25 Output relative to each node LPG wt.% 2.2 2.5 Naphtha wt.% 27.1 23.5 Middle distillate wt.% 50.7 61.0 Bottom residues wt.% 16.0 15.0 Yield relative to shale oil wt.% LPG wt.% 2.2 0.4 Naphtha wt.% 27.1 3.8 Middle distillate wt.% 50.7 9.8 Bottom residues wt.% 16.0 2.4 Total 80.0 13.9 (LPG + naphtha + middle distillate) / shale oil feed Total 93.9 (LPG + naphtha + middle distillate) / oil based on shale oil)

Claims (28)

1. The method of conversion of shale oil or a mixture of shale oils having a nitrogen content of at least 0.1 wt. %, characterized in that it contains the following stages:
a) the feed is introduced into the hydroconversion section in the presence of hydrogen, said portion comprising at least a fluidized bed reactor operating in a gaseous and liquid ascending mode and containing at least one hydroconversion catalyst on a support,
b) the effluent obtained in stage a) is introduced at least partially into the fractionation zone, from which, through atmospheric distillation, a gaseous fraction, a ligroin fraction, a gas oil fraction and a fraction heavier than the gas oil fraction exit
c) said ligroin fraction is processed at least partially in a first hydrotreatment portion in the presence of hydrogen, said portion comprising at least one fixed bed reactor comprising at least one hydrotreatment catalyst,
d) said gas oil fraction is processed at least partially in a second hydrotreatment part in the presence of hydrogen, said part comprising at least one fixed bed reactor comprising at least one hydrotreatment catalyst,
e) a fraction heavier than the gas oil fraction is treated at least partially in the hydrocracking portion in the presence of hydrogen. 2. The method according to p. 1, in which shale oil or a mixture of shale oils have a nitrogen content of at least 1 wt. % 3. The method according to p. 1, in which shale oil or a mixture of shale oils have a nitrogen content of at least 2 wt. % 4. The method according to claim 1, wherein in step b) the effluent obtained in step a) is introduced completely into the fractionation zone. 5. The method according to claim 1, wherein in step c) said ligroin fraction is completely processed in the first part for hydroprocessing in the presence of hydrogen. 6. The method according to claim 1, wherein in step d), said gas oil fraction is completely processed in the second part for hydroprocessing in the presence of hydrogen. 7. The method according to claim 1, wherein in step e) a fraction heavier than the gas oil fraction is processed completely in the hydrocracking portion in the presence of hydrogen. 8. The method of claim 1, wherein the hydrocracking effluents obtained at the end of step e) are fractionated into a second gaseous fraction, a second ligroin fraction, a second gas oil fraction, and a second heavier fraction than gas oil. 9. The method according to p. 8, in which the second fraction of naphtha is processed at least partially in part for hydroprocessing in stage c). 10. The method of claim 8, wherein the second gas oil fraction is processed at least partially in the hydrotreatment portion of step d). 11. The method according to p. 8, in which the second fraction, heavier than the gas oil fraction, is processed at least partially in part for hydroconversion in stage a). 12. The method of claim 1, wherein the hydrocracking effluents obtained at the end of step e) are separated into a gas oil fraction and a fraction lighter than gas oil and a fraction heavier than gas oil. 13. The method according to p. 12, in which the second fraction, heavier than gas oil, is processed at least partially in part for hydroconversion in stage a). 14. The method of claim 12, wherein the gas oil fraction and a fraction lighter than gas oil are introduced at least partially into the fractionation zone in step b). 15. The method of claim 8, wherein the second fraction, heavier than gas oil, is processed at least partially in the hydrocracking portion of step e). 16. The method of claim 1, wherein the effluent obtained in step a) is fractionated by atmospheric distillation into a gaseous fraction having a boiling point of less than 50 ° C., a ligroin fraction boiling at a temperature of from 50 ° C. to 150 ° C. a gas oil fraction boiling at a temperature of from 150 ° C to 370 ° C; and a fraction that is heavier than the gas oil fraction and which boils at a temperature above 340 ° C, preferably above 370 ° C. 17. The method according to claim 1, in which the parts for hydroprocessing with a fixed layer in stage c) and / or d) contain, upstream of the catalytic layers of the hydroprocessing, at least one specific protective layer for arsenic compounds and silicon compounds. 18. The method according to p. 1, in which the hydroconversion stage a) is carried out at a temperature of from 300 ° C to 550 ° C, at a total pressure of 2 to 35 MPa, with a mass hourly flow rate ((feed time / hour) / catalyst time) equal to from 0.2 to 1.5 h ^-1 , and with a hydrogen / feed ratio of from 50 to 5000 Nm ³ / m ³ . 19. The method according to p. 1, in which the hydroconversion stage a) is carried out at a temperature of from 400 ° C to 450 ° C, at a total pressure of 10 to 20 MPa, with a mass hourly flow rate ((feed time / hour) / catalyst time) equal to from 0.2 to 1.5 h ^-1 , and with a hydrogen / feed ratio of from 100 to 1000 Nm ³ / m ³ . 20. The method according to p. 1, in which the stage of hydroprocessing of the ligroin fraction c) is carried out at a temperature of from 280 ° C to 380 ° C, at a total pressure of 4 to 15 MPa, with a mass hourly flow rate ((feed time / hour) / time catalyst), equal to from 0.1 to 5 h ^-1 , and with a hydrogen / feed ratio of from 100 to 5000 Nm ³ / m ³ . 21. The method according to p. 1, in which the stage of hydroprocessing of the ligroin fraction c) is carried out at a temperature of from 300 ° C to 350 ° C, at a total pressure of 10 to 13 MPa, with a mass hourly flow rate ((raw material time / hour) / time catalyst), equal to from 0.1 to 5 h ^-1 , and with a hydrogen / feed ratio of from 100 to 1000 Nm ³ / m ³ . 22. The method according to p. 1, in which the stage of hydroprocessing of the gas oil fraction d) is carried out at a temperature of from 320 ° C to 450 ° C, at a total pressure of 7 to 20 MPa, with a mass hourly flow rate ((feed time / hour) / time catalyst), equal to from 0.1 to 1 h ^-1 , and with a hydrogen / feed ratio of from 100 to 5000 Nm ³ / m ³ . 23. The method according to p. 1, in which the stage of hydroprocessing of the gas oil fraction d) is carried out at a temperature of from 340 ° C to 400 ° C, at a total pressure of 10 to 15 MPa, with a mass hourly flow rate ((feed time / hour) / time catalyst), equal to from 0.3 to 0.8 h ^-1 , and with a hydrogen / feed ratio of 200 to 1000 Nm ³ / m ³ . 24. The method according to p. 1, in which the stage of hydrocracking of a fraction heavier than gas oil, e) is carried out at a temperature of from 350 ° C to 450 ° C, at a total pressure of 10 to 20 MPa, at a mass hourly rate ((time raw materials / hour) / catalyst time), equal to from 0.3 to 7 h ^-1 , and with a hydrogen / raw material ratio of from 100 to 5000 Nm ³ / m ³ . 25. The method according to p. 1, in which the stage of hydrocracking of a fraction heavier than gas oil, e) is carried out at a temperature of from 370 ° C to 425 ° C, at a total pressure of 15 to 18 MPa, at a mass hourly rate ((time raw materials / hour) / catalyst time), equal to from 0.5 to 1.5 h ^-1 , and with a hydrogen / raw material ratio of from 1000 to 2000 Nm ³ / m ³ . 26. The method according to p. 1, in which the catalysts in the hydroconversion stage a) and the hydroprocessing stages c) and d), the hydrocracking stages e) are independently selected from the group of catalysts containing a metal of group VIII selected from the group consisting of Ni and / or Co, if necessary, a metal of group VIB selected from the group consisting of Mo and / or W on an amorphous substrate selected from the group consisting of aluminum oxide, silicon oxide, aluminosilicates, magnesium oxide, clays and mixtures thereof, or on a substrate, containing at least partially zeolite material. 27. The method according to any of the preceding paragraphs, in which shale oil or a mixture of shale oils is provided from hydrocarbon materials selected from the group consisting of oils derived from coal, oils derived from heavy resins and tar sand, vacuum distillates and direct distillation residues , vacuum distillates and non-converted residues obtained from the processing of fuel oil, oils deasphalted with solvents, light cyclic oils, heavy cyclic oils, gas oil fractions originating from catalytic cracking and, as a rule, having a boiling range of fractions from 150 ° C to 650 ° C, aromatic extracts obtained in the production of lubricating oils, pyrolytic oils of wood residues, such as wood residues, crude oil derived from biomass ("bio-raw materials" ), vegetable oils and animal fats, or mixtures of such raw materials. 28. Installation for processing shale oil by the method according to any one of paragraphs. 1-27, containing:
- part for hydroconversion in the presence of hydrogen, containing a fluidized bed reactor operating in a gaseous and liquid upward flow mode and containing at least one hydroconversion catalyst on a substrate,
- fractionation zone through atmospheric distillation,
- the first part for hydroprocessing in the presence of hydrogen, containing a fixed-bed reactor containing at least one hydroprocessing catalyst,
- the second part for hydroprocessing in the presence of hydrogen, containing at least one fixed-bed reactor containing at least one hydroprocessing catalyst,
- part for hydrocracking in the presence of hydrogen.

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