Hydrocracking catalysts for naphtha production containing zeolite Y and zeolite beta with Y / beta ratio strictly higher than 12.

Abstract

The present invention describes a hydrocracking catalyst selective towards naphtha fractions and a hydrocracking process utilizing said catalyst, said catalyst comprising at least one hydrodehydrogenating element selected alone or in a mixture from the group consisting of the elements of group VIB and non-noble group VIII of the periodic table, and a support comprising at least one porous mineral matrix, zeolite Y, the initial lattice parameter a0 of the unit cell being greater than 24.42A, and zeolite beta, the weight ratio of said zeolite Y to said zeolite beta in the catalyst being strictly greater than 12.

Description

[Technical field]

[0001] The present invention relates to a hydrocracking catalyst based on zeolites Y and Beta and also to its use for the production of naphtha by hydrocracking of petroleum fractions of the vacuum distillate or gas oil type. This type of process is used in schemes aimed at the conversion of hydrocarbon feedstocks for the production of petrochemical intermediates and gasoline fuels, among others. [Background technology]

[0002] Hydrocracking catalysts are generally classified on the basis of the nature of their acid functionality, in particular catalysts containing amorphous acid functionality of the silica-alumina type and catalysts containing zeolitic cracking functionality, e.g. zeolite Y or zeolite beta.

[0003] Hydrocracking catalysts are also classified by the primary products obtained when they are used in hydrocracking processes, the two primary products being middle distillates and naphtha.

[0004] Naphtha or naphtha fraction is understood to mean a petroleum fraction having a boiling point lower than the middle distillate fraction. The middle distillate fraction generally has a cut point between 150° C. and 370° C., which maximizes the production of kerosene and gas oil. However, the lower cut point of the middle distillate fraction may be increased to improve the naphtha yield, for example in the case of a process specifically targeted at the production of naphtha.

[0005] For this purpose, naphtha fractions can have boiling points between the boiling point of hydrocarbon compounds having six carbon atoms per molecule (or 68°C boiling point) and 216°C, and include gasoline fractions.

[0006] There is high demand for gasoline and naphtha fractions, which is why refiners have been focusing for several years on hydrocracking catalysts that are selective towards naphtha fractions.

[0007] It is known to produce naphtha fractions using catalysts based on FAU type zeolites.

[0008] Patent document 1 (Shell) describes zeolite Y of the FAU type, a catalyst containing said zeolite, its preparation and its use in hydrocracking processes. In particular, the lattice parameter of FAU zeolite is 24.40-24.50 angstroms (Å), the silica to alumina molar ratio (SAR) is 5-10 and the alkali metal content is less than 0.15% by weight. Such zeolites have been demonstrated to have high selectivity towards naphtha fractions, in particular towards heavy naphtha fractions, when they are used in hydrocracking processes.

[0009] Other catalysts based on zeolite Y and zeolite beta may also be used.

[0010] UOP describes a hydrocracking catalyst containing zeolite beta and zeolite Y, the lattice constant of zeolite Y being 24.38-24.50 angstroms (Å), the catalyst being characterized by a weight ratio of Y / beta being 5-12. The proportion of zeolite Y in the catalyst is relatively high compared to the proportion of zeolite beta. These catalysts have been demonstrated to have improved selectivity and activity compared to conventional commercial catalysts. Also disclosed is a hydrocracking process using said catalyst at high temperature and pressure to convert a hydrocarbon feedstock into products having lower boiling points and lower molecular weights. In particular, the resulting products contain a majority of components boiling in the naphtha fraction temperature range (C6-216°C).

[0011] While trying to develop a new hydrocracking catalyst selective towards naphtha fractions, the Applicant has surprisingly discovered that a catalyst comprising at least one hydrodehydrogenating element selected from the group formed by the elements of group VIB and the non-noble metal elements of group VIII of the periodic table, and a support comprising at least one porous mineral matrix, a zeolite Y having an initial lattice parameter a0 of the unit cell greater than 24.42 Å, and a zeolite Beta, the weight ratio of said zeolite Y to said zeolite Beta being strictly greater than 12, makes it possible to obtain an improved selectivity towards naphtha fractions, in particular compared to the catalysts of the prior art. [Prior art documents] [Patent documents]

[0012] [Patent Document 1] U.S. Patent No. 7,611,689 [Patent Document 2] U.S. Patent No. 7,510,645 Summary of the Invention [Means for solving the problem]

[0013] (Subject of the Invention) More specifically, the present invention relates to a hydrocracking catalyst selective for naphtha fractions, comprising at least one hydrodehydrogenating element selected from the group formed by the elements of group VIB and the non-noble metal elements of group VIII of the periodic table, employed alone or in a mixture, and a support comprising at least one porous mineral matrix, a zeolite Y having an initial lattice parameter a0 of the unit cell greater than 24.42 Å, and a zeolite beta, the weight ratio of said zeolite Y to said zeolite beta in the catalyst being strictly greater than 12.

[0014] The present invention relates to a hydrocracking catalyst comprising at least one hydrodehydrogenating element, advantageously selected from the group formed by the elements of group VIB and the non-noble metal elements of group VIII of the periodic table, employed alone or in a mixture, and a support comprising at least one porous mineral matrix, a zeolite Y having an initial lattice parameter a0 of the unit cell greater than 24.42 Å, and a zeolite beta, the weight ratio of said zeolite Y to said zeolite beta in the catalyst being greater than 12.

[0015] The present invention relates to a hydrocracking catalyst comprising at least one hydrodehydrogenating element, employed alone or in a mixture, advantageously selected from the group formed by the elements of group VIB and the non-noble metal elements of group VIII of the periodic table, and a support comprising at least one porous mineral matrix, a zeolite Y having an initial lattice parameter a0 of the unit cell greater than 24.42 Å, and a zeolite beta, the weight ratio of said zeolite Y to said zeolite beta in the catalyst being greater than 12.

[0016] The present invention relates to a hydrocracking catalyst comprising at least one hydrodehydrogenating element, advantageously selected from the group formed by the elements of group VIB and the non-noble metal elements of group VIII of the periodic table, employed alone or in a mixture, and a support comprising at least one porous mineral matrix, zeolite Y and zeolite beta, the weight ratio of said zeolite Y to said zeolite beta in the catalyst being greater than 12.

[0017] This weight ratio is calculated from the dry weight of the zeolites, ie the weight of the zeolites (dry weight) corrected for their water content determined by measuring the loss on ignition at 1000°C.

[0018] Another subject of the invention is a process for hydrocracking a hydrocarbon feedstock in the presence of said catalyst.

[0019] One advantage of the present invention is that it provides a hydrocracking catalyst for obtaining improved selectivity towards naphtha fractions compared to catalysts from the prior art when said catalyst is used in the hydrocracking process according to the invention.

[0020] In the present invention, the selectivity of the hydrocracking catalyst for naphtha production is determined during the catalytic test and corresponds to the proportion of naphtha fraction, i.e. products boiling in the range between the boiling temperature of hydrocarbon compounds having 6 carbon atoms per molecule (or 68°C boiling point) up to 216°C, as a weight percentage relative to the total weight of products leaving the process.

[0021] For the purposes of the present invention, the various embodiments presented may be used alone or in combination with each other, without any limitations on combinations.

[0022] For purposes of the present invention, various ranges of parameters for a given process, such as pressure ranges and temperature ranges, may be used alone or in combination, e.g., for purposes of the present invention, a preferred range of pressure values ​​may be combined with a more preferred range of temperature values.

[0023] In the following text, the groups of chemical elements are given according to the CAS classification (CRC Handbook of Chemistry and Physics, published by CRC Press, editor DR Lide, 81st edition, 2000-2001). For example, group VIII according to the CAS classification corresponds to metals from columns 8, 9 and 10 according to the new IUPAC classification, and group VIB corresponds to metals from column 6.

[0024] In the text that follows, the expressions "of between A and B" and "between A and B" are equivalent and mean that both limits of the interval (A, B) are included in the stated range of both values. If this is not the case and if both limits are not included in the stated range, such an explanation is given by the present invention. DETAILED DESCRIPTION OF THE PREFERRED EMBODIMENTS

[0025] Detailed Description of the Invention (hydrogenation / dehydrogenation function) According to the invention, the catalyst comprises at least one hydrodehydrogenating element selected from the group formed by the elements of group VIB and the non-noble metal elements of group VIII of the periodic table, used alone or in a mixture.

[0026] Preferably, the catalyst according to the invention comprises an active phase which comprises, preferably consists of, at least one metal of group VIB and at least one metal of group VIII.

[0027] Preferably, the group VIII elements are selected from iron, cobalt and nickel, used alone or as a mixture, preferably nickel and cobalt. Preferably, the group VIB elements are selected from tungsten and molybdenum, used alone or as a mixture. The following combinations of metals are suitable: nickel-molybdenum, cobalt-molybdenum, nickel-tungsten, cobalt-tungsten, highly preferred: nickel-molybdenum, nickel-tungsten. It is also possible to use combinations of three metals, for example nickel-cobalt-molybdenum.

[0028] The content of group VIII elements in the catalyst is advantageously between 0.5% and 8% by weight of oxide, preferably between 0.5% and 6% by weight of oxide, highly preferably between 1.0% and 4% by weight of oxide relative to the total weight of said catalyst. The content of group VIB metals in the catalyst is advantageously between 1% and 30% by weight of oxide, preferably between 2% and 25% by weight of oxide, highly preferably between 5% and 20% by weight of oxide, even more preferably between 5% and 16% by weight of oxide, relative to the total weight of said catalyst.

[0029] Preferably, the catalyst used according to the invention can also contain a promoter element selected from phosphorus, boron, silicon, highly preferably phosphorus. When the catalyst contains phosphorus, the phosphorus content is advantageously between 0.5% and 10% by weight of P2O5 oxide relative to the total weight of the catalyst, preferably between 1% and 6% by weight of P2O5 oxide relative to the total weight of the catalyst, more preferably between 1% and 4% by weight of P2O5 oxide.

[0030] (Carrier) The support contained in the catalyst according to the invention comprises, and preferably consists of, at least one porous mineral matrix, zeolite Y having an initial lattice parameter a0 of the unit cell greater than 24.42 Å, and zeolite beta.

[0031] The porous mineral matrix used in the support of the catalyst, also called binder, advantageously consists of at least one refractory oxide, preferably selected from the group formed by alumina, silica-alumina, clay, titanium oxide, boron oxide and zirconia, used alone or as a mixture. Preferably, the porous mineral matrix is ​​selected from alumina and silica-alumina, used alone or as a mixture. More preferably, the porous mineral matrix is ​​alumina. The alumina can advantageously be in any of its forms known to the skilled person. Highly preferably, the alumina is gamma alumina, for example boehmite.

[0032] Preferably, the support comprises from 14% to 48% by weight, preferably from 15% to 40% by weight, highly preferably from 20% to 40% by weight, of a binder relative to the total weight of the support.

[0033] According to the invention, the support comprises zeolite Y, the unit cell of which has an initial lattice parameter a0 greater than 24.42 Å.

[0034] Preferably, the initial lattice parameter a0 of the unit cell of the zeolite Y used is between 24.42 Å and 24.70 Å, preferably between 24.45 Å and 24.70 Å, preferably between 24.50 Å and 24.70 Å, preferably between 24.52 Å and 24.70 Å, preferably between 24.52 Å and 24.65 Å, preferably between 24.52 Å and 24.60 Å, highly preferably between 24.52 Å and 24.58 Å.

[0035] The initial lattice parameter a0 of the unit cell of a given zeolite Y is the value of the initial lattice parameter a0 of the zeolite Y used in the synthesis of the catalyst according to the invention.

[0036] The initial lattice parameter a0 of the unit cell of zeolite Y is determined by X-ray diffraction according to standard ASTM 03942-80.

[0037] Preferably, the total content of zeolite Y in the support is between 50% and 80% by weight, preferably between 50% and 70% by weight, preferably between 55% and 65% by weight relative to the total weight of the support.

[0038] Said zeolites are advantageously defined in the classification "Atlas of Zeolite Framework Types", 6th Revised Edition", Ch. Baerlocher, LB McCusker, DH Olson, 6th Edition, Elsevier, 2007, Elsevier.

[0039] According to a preferred embodiment of the invention, the zeolite Y having the specific characteristics defined above that make it suitable for use as a catalyst support in the process according to the invention is advantageously prepared from a zeolite Y of FAU structure type, preferably having an overall Si / Al atomic ratio of 2.3 to 2.8 after synthesis and advantageously of NaY type after synthesis. Said zeolite Y of FAU structure type advantageously undergoes one or more steps of ion exchange before undergoing a dealumination step, by which the alkali cations belonging to groups IA and IIA of the periodic table present in the cation positions in the crudely synthesized zeolite Y of FAU structure type are partially or completely replaced by NH4 + Cation, preferably Na + Cation to NH4 + It becomes possible to substitute with a cation.

[0040] Alkaline cation NH4 + The partial or complete exchange with cations is from 80% to 100%, preferably from 85% to 99.5%, more preferably from 88% to 99% of the alkali cations with NH4. + It is understood to mean the exchange with cations. At the end of one or more ion exchange steps, the remaining amount of alkali cations in the zeolite Y, preferably Na + The residual amount of cations is the amount of alkali cations initially present in the zeolite Y, preferably Na + Relative to the amount of cations, it is advantageously between 0% and 20%, preferably between 0.5% and 15%, preferably between 1.0% and 12%.

[0041] Preferably, this step involves multiple ion exchanges with a solution containing at least one ammonium salt selected from ammonium chlorate, sulfate, nitrate, phosphate or acetate, to remove the alkali cations present in the zeolite, preferably Na + The cations are at least partially removed. Preferably, the ammonium salt is ammonium nitrate NH4NO3.

[0042] Therefore, the alkali cations in the zeolite Y at the end of one or more ion exchange steps, preferably Na + The residual content of cations is preferably such that the molar ratio of alkali cation / aluminium, preferably the molar ratio of Na / Al, is 0:1 to 0:1, preferably 0:1 to 0.005:1, more preferably 0:1 to 0.008:1.

[0043] The desired ratio of alkali cation / aluminum, preferably Na / Al, is determined by the NH4 + The concentration of NH4 in the ion exchange solution can be adjusted by adjusting the ion exchange temperature and the number of ion exchanges. + The concentration is advantageously less than 0.01 mol L -1 and 12 mol L -1 Between 1.00 and 1.00 mol L -1 and 10 mol L -1 The temperature of the ion exchange step advantageously varies between 20° C. and 100° C., preferably between 60° C. and 95° C., preferably between 60° C. and 90° C., more preferably between 60° C. and 85° C., even more preferably between 60° C. and 80° C. The number of ion exchanges advantageously varies between 1 and 10, preferably between 1 and 4.

[0044] The zeolite Y obtained, preferably of structure type FAU, can then undergo a dealumination step which may advantageously be carried out by any method known to the person skilled in the art. Preferably, the dealumination is carried out by a thermal treatment, optionally in the presence of water vapor (or "steaming") and / or by one or more acid attacks, advantageously by treatment with an aqueous solution of a mineral or organic acid.

[0045] Preferably, the dealumination step involves a heat treatment followed by one or more acid attacks, or only one or more acid attacks.

[0046] Preferably, the temperature at which the heat treatment, optionally in the presence of water vapor, to which the zeolite Y is subjected, is between 200° C. and 900° C., preferably between 300° C. and 900° C., and even more preferably between 400° C. and 750° C. The duration of the heat treatment is advantageously greater than or equal to 0.5 h, preferably between 0.5 h and 24 h, and highly preferably between 1 h and 12 h. In the case where the heat treatment is performed in the presence of water, the volume percentage of water vapor during the heat treatment is advantageously between 5% and 100%, preferably between 20% and 100%, and highly preferably between 40% and 100%. Any volume part present that is not water vapor is formed from air. The flow rate of the gas formed from water vapor and optionally air is advantageously less than 0.2 L·h -1 ·g -1 ~10L·h -1 ·g -1 (Zeolite Y).

[0047] The heat treatment allows the extraction of aluminum atoms from the structure of zeolite Y while keeping the overall Si / Al atomic ratio of the treated zeolite unchanged.

[0048] The step of heat treatment in the presence of water vapor may be advantageously repeated as many times as necessary to obtain a zeolite Y suitable for carrying the catalyst used in the process according to the invention and having a lattice parameter a0 of the unit cell greater than 24.42 Å.

[0049] The step of heat treatment, optionally in the presence of water vapor, is advantageously followed by a step of acid attack, which makes it possible to partially or completely remove aluminate debris resulting from the step of heat treatment in the presence of water vapor that may partially block the porosity of the dealuminated zeolite; the acid attack thus makes it possible to unblock the porosity of the dealuminated zeolite.

[0050] The acid attack may advantageously be carried out by suspending the zeolite Y, which may have undergone a prior heat treatment, in an aqueous solution containing a mineral or organic acid. The mineral acid may be nitric acid, sulphuric acid, hydrochloric acid, phosphoric acid or boric acid. The organic acid may be formic acid, acetic acid, oxalic acid, tartaric acid, maleic acid, malonic acid, malic acid, lactic acid or any other water-soluble organic acid. The concentration of the mineral or organic acid in the solution is advantageously less than 0.01 mol L -1 and 2.0 mol L -1 Between 0.5 and 1.5 mol L -1 and 1.0 mol L -1 The temperature of the acid attack step is advantageously between 20° C. and 100° C., preferably between 60° C. and 95° C., preferably between 60° C. and 90° C., more preferably between 60° C. and 80° C. The duration of the acid attack is advantageously between 5 minutes and 8 hours, preferably between 30 minutes and 4 hours, preferably between 1 hour and 2 hours.

[0051] Upon completion of the step or steps of heat treatment, optionally in the presence of water vapor, and the optional acid attack step, said method for modifying zeolite Y advantageously comprises removing the alkali cations still present in the cation sites in the zeolite Y, preferably Na + The ion exchange step is carried out in a manner similar to the ion exchange step described above.

[0052] Optionally, one or more steps of heat treatment in the presence of water vapor and an optional acid attack step and optionally an alkali cation, preferably Na + At the end of the step of partial or complete exchange of cations, the method for modifying the zeolite Y may include a calcination step, which makes it possible to remove organic species present in the zeolite porosity, such as those provided by the acid attack step or the step of partial or complete exchange of alkali cations, and in addition makes it possible to generate the proton form of the zeolite Y and to make it acidic for the purposes of its application.

[0053] The calcination may advantageously be carried out in a muffle or tubular furnace, under dry air or under an inert atmosphere, in a swept or transverse bed. The calcination temperature is advantageously between 200° C. and 800° C., preferably between 450° C. and 600° C., preferably between 500° C. and 550° C. The duration of the calcination held is advantageously between 1 and 20 hours, preferably between 6 and 15 hours, preferably between 8 and 12 hours.

[0054] Therefore, the initial lattice parameter a of the resulting zeolite Y unit cell is greater than 24.42 Å.

[0055] The resulting zeolite Y advantageously has a specific surface area, measured by nitrogen physisorption according to the BET method, of between 550 and 1000 m 2 / g, preferably 600 to 900m 2 / g, preferably 650 to 800m 2 / g.

[0056] According to the present invention, the support also comprises zeolite beta.

[0057] Zeolite beta is generally synthesized from a reaction mixture containing a structuring agent. The use of structuring agents is well known to those skilled in the art: for example, patent US 3,308,069 describes the use of tetraethylammonium hydroxide, and patent US 5,139,759 describes the use of tetraethylammonium cations derived from tetraethylammonium chloride compounds. Another standard method for preparing zeolite beta is given in the book "Verified Synthesis of Zeolitic Materials".

[0058] The zeolite beta used in the support according to the invention preferably has an overall SAR atomic ratio of between 10 and 100, preferentially between 20 and 50, more preferably between 20 and 30. The zeolite beta used in the support according to the invention advantageously has a specific surface area, measured by nitrogen physisorption according to the BET method, of between 400 and 800 m 2 / g, preferably 500 to 750m2 / g, preferably 550 to 700m 2 / g.

[0059] Preferably, the zeolite beta content of the support is between 2% and 6%, preferably between 2% and 5%, preferably between 3% and 5%, by weight relative to the total weight of said support.

[0060] Preferably, the carrier comprises, preferably consists of: - zeolite Y whose unit cell has an initial lattice parameter a0 strictly greater than 24.50 Å: from 50% to 80%, preferably from 50% to 70%, preferably from 55% to 65%, by weight relative to the total weight of the support; - Zeolite beta: 2% to 6%, preferably 2% to 5%, or 3% to 5%, by weight relative to the total weight of the support; and - at least one porous mineral matrix: from 14% to 48% by weight, preferably from 15% to 40% by weight, highly preferably from 20% to 40% by weight, the weight of which is relative to the total weight of said support;

[0061] According to the invention, the weight ratio of said zeolite Y to said zeolite beta in the catalyst is strictly greater than 12.

[0062] Preferably, the weight ratio of said zeolite Y to said zeolite beta in the catalyst is 13-40, preferably 13-30, preferably 14-20, even more preferably 14-18.

[0063] Preferably, the zeolite Y content of the catalyst is between 26% and 79% by weight relative to the total weight of said catalyst.

[0064] Preferably, the zeolite beta content of the catalyst is between 1% and 6% by weight relative to the total weight of the catalyst.

[0065] Preferably, the content of at least one porous mineral matrix in said catalyst is between 7% and 47% by weight relative to the total weight of said catalyst.

[0066] The Y / Beta ratios within these ranges of the hydrocracking catalysts according to the invention make it possible to obtain improved selectivity towards naphtha fractions when said catalysts are used in the hydrocracking process according to the invention, compared to catalysts from the prior art.

[0067] (Catalyst Preparation) The catalyst is advantageously prepared by conventional methods used in the art.

[0068] In particular, the catalyst is prepared by a preparation method comprising the following steps: - preparing the carrier; comprising: mixing at least one porous mineral matrix with a zeolite Y and a zeolite beta, the unit cell of which has an initial lattice parameter a0 greater than 24.42 Å; the weight ratio of said zeolite Y to said zeolite beta in the catalyst is strictly greater than 12, preferably between 13 and 40, preferably between 13 and 30, preferably between 14 and 20, even more preferably between 14 and 18, and forming the mixture; - introducing on the support at least one hydrodehydrogenating element selected from the group formed by the elements of group VIB of the periodic table, preferably nickel and cobalt, the non-noble metal elements of group VIII of the periodic table, preferably iron, cobalt, nickel, and mixtures thereof, preferably nickel and cobalt, and mixtures thereof; adding at least one precursor of said element during shaping so as to incorporate at least a portion of said element, impregnating the support with at least one precursor of said element, an optional step of drying and / or calcining at the end of the preparation of the support and / or of introducing at least one hydrodehydrogenating element.

[0069] More specifically, the catalyst is prepared according to a preparation method comprising the following steps: a) preparing a zeolite Y having the specific crystallographic characteristics claimed by the above process, b) preparing zeolite beta; c) mixing with a porous mineral matrix and shaping to obtain a carrier; d) introducing at least one hydrodehydrogenating element onto the support by at least one of the following methods: - adding at least one precursor of said element during shaping to introduce at least a portion of said element, impregnating a support with at least one precursor of said hydrodehydrogenating element, Optionally, at the end of each of the preparation steps a) or b) or c) or d) a drying and / or calcination of the product obtained is carried out.

[0070] The carrier may advantageously be shaped by any technique known to those skilled in the art, for example by extrusion, pelletization, the drop congealing (oil drop) method, granulation on a rotating plate or any other method known to those skilled in the art.

[0071] The supports are preferably formed in the form of granules of various shapes and sizes. They are generally used in the form of cylindrical extrudates or multilobal extrudates, for example trilobal, tetralobal or multilobal, of straight or twisted shape, but can also be produced and used in the form of crushed powders, troches, rings, beads or wheels. However, it is advantageous for the catalyst to be in the form of extrudates with a diameter of 0.5 to 5 mm, more particularly 0.7 to 3 mm, monolayer and more particularly 1.0 to 2.5 mm. The shape is cylindrical (which may or may not be hollow), twisted cylindrical, multilobal (for example 2, 3, 4 or 5 lobes) or annular. Any other shape may be used.

[0072] One suitable shaping method consists in co-kneading both said zeolites with a binder, preferably alumina, in the form of a wet gel for a few tens of minutes, preferably between 10 and 40 minutes, then forcing the paste thus obtained through a die to form extrudates with a diameter preferably between 0.5 and 5 mm.

[0073] According to another of the preferred forming methods, the two zeolites can be introduced during the synthesis of the porous mineral matrix. For example, according to this preferred embodiment of the invention, the zeolites Y and beta are added during the synthesis of the porous mineral matrix, such as a silicoaluminate matrix: in this case, the two zeolites can advantageously be added to a mixture of an alumina compound and a completely soluble silica compound in an acid medium.

[0074] The elements of Group VIB and / or Group VIII may optionally be introduced by adding at least one compound of said elements during the shaping step to introduce at least a portion of said elements.

[0075] The introduction of at least one hydrodehydrogenating element may advantageously be accompanied by the introduction of at least one promoter element selected from phosphorus, boron, silicon, preferably phosphorus, and optionally by the introduction of an element of group VIIA and / or group VB. The shaped solid is optionally dried at a temperature between 60° C. and 250° C. and optionally calcined at a temperature between 250° C. and 800° C. for a period between 30 minutes and 6 hours.

[0076] The step of introducing at least one hydrodehydrogenating element is advantageously carried out by methods known to those skilled in the art, in particular by one or more operations of impregnating the shaped and calcined or dried, preferably calcined, support with a solution containing precursors of an element of group VIB and / or group VIII, optionally a precursor of at least one promoter element and optionally a precursor of at least one element of group VIIA and / or group VB.

[0077] Preferably, said step d) is carried out by a method of dry impregnation of a solution containing hydrogenation / dehydrogenation functional groups, i.e. precursors of elements of group VIB and / or group VIII, optionally followed by a drying step and preferably without a calcination step.

[0078] In cases where the catalyst of the invention contains a non-noble Group VIII metal, the Group VIII metal is preferably introduced by one or more operations of impregnation of the shaped and calcined support, either after or simultaneously with the Group VIB operation.

[0079] The introduction of at least one hydrogenating / dehydrogenating element can optionally be followed by drying at a temperature between 60°C and 250°C and, optionally, by calcination at a temperature between 250°C and 800°C.

[0080] The sources of molybdenum and tungsten are advantageously selected from the oxides and hydroxides, molybdic and tungstic acids and their salts, in particular the ammonium salts, such as ammonium molybdate, ammonium heptamolybdate and ammonium tungstate, phosphomolybdic acid, phosphotungstic acid and their salts, silicomolybdic acid, silicotungstic acid and their salts. Use is preferably made of the oxides and ammonium salts, such as ammonium molybdate, ammonium molybdate, ammonium heptamolybdate and ammonium tungstate.

[0081] Sources of non-noble Group VIII elements that may be used are well known to those skilled in the art. For example, for non-noble metals, use may be made of nitrates, sulfates, hydroxides, phosphates, halides such as chlorides, bromides and fluorides, carboxylates such as acetates and carbonates.

[0082] The preferred source of phosphorus is orthophosphoric acid H3PO4, but its salts and esters, such as ammonium phosphate, are also suitable.Phosphorus may be introduced, for example, in the form of a mixture of phosphoric acid with nitrogen-containing basic organic compounds, such as aqueous ammonia, primary and secondary amines, cyclic amines, compounds of the pyridine and quinoline series, and compounds of the pyrrole series.Tungstophosphoric acid or tungstomolybdic acid may be used.

[0083] The phosphorus content is adjusted to form mixed compounds, such as tungsten-phosphorus or molybdenum-tungsten-phosphorus, in the solution and / or on the support, but this is not intended to limit the scope of the present invention. These mixed compounds can be heteropolyanions. These compounds can be, for example, Anderson heteropolyanions.

[0084] The source of boron may be boric acid, preferably orthoboric acid H3BO3, ammonium diborate or ammonium pentaborate, boron oxide or boric acid ester. Boron may be introduced, for example, in the form of a mixture of boric acid, aqueous hydrogen peroxide and nitrogen-containing basic organic compounds, such as aqueous ammonia, primary and secondary amines, cyclic amines, compounds of the pyridine and quinoline series and compounds of the pyrrole series. Boron may be introduced, for example, by a solution of boric acid in a water / alcohol mixture.

[0085] Many silicon sources may be used. Thus, use may be made of ethyl orthosilicate Si(OEt)4, siloxanes, polysiloxanes, silicones, silicone emulsions, silica halide, such as ammonium fluorosilicate (NH4)2SiF6 or sodium fluorosilicate Na2SiF6. Silicomolybdic acid and its salts, silicotungstic acid and its salts may also be advantageously used. Silicon may be advantageously added, for example, by impregnation with a solution of ethyl silicate in a water / alcohol mixture. Silicon may be added, for example, by impregnation with a silicon compound of silicone or silicic acid type suspended in water.

[0086] The sources of group VB elements that can be used are well known to those skilled in the art. For example, among the sources of niobium, use may be made of oxides such as diniobium pentoxide Nb2O5, niobate Nb2O5·H2O, niobium hydroxide and polyoxoniobates, niobium alkoxides of formula Nb(OR1)3 (wherein R1 is an alkyl group), niobium oxalate NbO(HC2O4)5, or ammonium niobate. Use is preferably made of niobium oxalate or ammonium niobate.

[0087] The sources of group VIIA elements that can be used are well known to those skilled in the art. For example, fluoride anions can be introduced in the form of hydrofluoric acid or its salts. These salts are formed with alkali metals, ammonium or organic compounds. In the case of organic compounds, the salts are advantageously formed in the reaction mixture by reaction between the organic compound and hydrofluoric acid. It is also possible to use hydrolyzable compounds capable of releasing fluoride anions in water, such as ammonium fluorosilicate (NH4)2SiF6, silicon tetrafluoride SiF4 or sodium tetrafluoride Na2SiF6. Fluorine can be introduced, for example, by impregnation with an aqueous solution of hydrofluoric acid or ammonium fluoride.

[0088] (hydrocracking method) The catalyst according to the invention is advantageously used in hydrocracking processes, in particular for the production of naphtha. The catalyst used in hydrocracking processes, such as the process according to the invention, can advantageously be in sulfided form. The Group VIB metals and / or non-noble Group VIII metals of said catalyst are therefore present in sulfided form.

[0089] The catalysts used in the process according to the invention are advantageously subjected to a prior sulfurization treatment in order to convert, at least in part, the metallic species into the sulfurized form before they are brought into contact with the feedstock to be treated. This activation treatment by sulfurization can be carried out in situ, i.e. in the reactor, or ex situ, by any of the methods well known to the person skilled in the art and already described in the literature.

[0090] Conventional sulfurization processes well known to those skilled in the art consist of heating the catalyst in the presence of hydrogen sulfide (high purity or, for example, under a flow of hydrogen-hydrogen sulfide mixture) at temperatures between 150° C. and 800° C., preferably between 250° C. and 600° C., typically in a flow-through bed reaction zone.

[0091] Another subject of the invention is a process for hydrocracking at least one hydrocarbon feedstock, preferably in liquid form, in which at least 50% by weight of the compounds of said feedstock have an initial boiling point above 300° C. and a final boiling point below 650° C., said hydrocracking being carried out in the presence of a catalyst according to the invention, in which the temperature is between 200° C. and 480° C., in which the total pressure is between 1 MPa and 25 MPa, in which the volume ratio of hydrogen per volume of hydrocarbon feedstock is between 80 and 5000 liters / liter, in which the hourly space velocity (HSV), defined by the ratio of the volumetric flow rate of the hydrocarbon feedstock, which is preferably liquid, per volume of catalyst charged in the reactor, is between 0.1 and 50 h . -1 It is.

[0092] Advantageously, the catalyst according to the invention is used in the hydrocracking process according to the invention after a pretreatment section containing one or more hydrotreating catalysts, which may be any catalyst known to the skilled artisan and which makes it possible to reduce the content of certain pollutants, such as nitrogen, sulfur or metals, in the feedstock (see below). The operating conditions of this pretreatment section (HSV, temperature, pressure, hydrogen flow rate, liquids, reaction configuration, etc.) may vary widely according to the knowledge of the skilled artisan.

[0093] (Feed material) A wide variety of feedstocks can be processed by the hydrocracking process according to the invention. The feedstock used in the hydrocracking process according to the invention is a hydrocarbon feedstock, in which at least 50% by weight of the compounds have an initial boiling point above 300° C. and a final boiling point below 650° C., preferably at least 60% by weight of the compounds, preferably at least 75% by weight of the compounds, more preferably at least 80% by weight of the compounds have an initial boiling point above 300° C. and a final boiling point below 650° C.

[0094] The feedstocks are advantageously chosen from LCO (Light Cycle Oil, light gas oils obtained from catalytic cracking units), atmospheric distillates, vacuum distillates, for example gas oils obtained from direct distillation of crude oil or from conversion units, for example FCC, coking or visbreaking units, feedstocks originating from units for the extraction of aromatics from lubricant base stocks or feedstocks resulting from the solvent dewaxing of lubricant base stocks, distillates originating from processes for the fixed or ebullated bed desulfurization or hydroconversion of AR (atmospheric residues) and / or VR (vacuum residues) and / or deasphalted oils, and paraffins obtained from the Fischer-Tropsch process, used alone or as a mixture. Mention may be made of feedstocks of renewable origin (for example vegetable oils, animal fats, oils from the hydrothermal conversion or pyrolysis of lignocellulosic biomass), and also plastic pyrolysis oils. The above list is not limiting. The boiling point T5 of said feedstock is preferably above 300°C, preferably above 340°C, i.e. 95% of the compounds present in the feedstock have a boiling point above 300°C, preferably above 340°C.

[0095] The nitrogen content of the feedstock treated in the process according to the invention is advantageously greater than 500 ppm by weight, preferably between 500 and 10,000 ppm by weight, more preferably between 700 and 4000 ppm by weight, even more preferably between 1000 and 4000 ppm by weight. The sulphur content of the feedstock treated in the process according to the invention is advantageously between 0.01% and 5% by weight, preferably between 0.2% and 4% by weight, even more preferably between 0.5% and 3% by weight.

[0096] The feedstock may optionally contain metals. The cumulative nickel and vanadium content of the feedstock treated in the process according to the invention is preferably less than 1 ppm by weight.

[0097] The feedstock may optionally contain asphaltenes. The asphaltene content is generally less than 3000 ppm by weight, preferably less than 1000 ppm by weight, and even more preferably less than 200 ppm by weight.

[0098] Advantageously, when the catalyst according to the invention is used after the hydrotreating section described above, the nitrogen, sulfur, metal or asphaltene content in the liquid injected into the process according to the invention using the catalyst according to the invention is reduced. Preferably, the organic nitrogen content in the feedstock treated in the hydrocracking process according to the invention is then, after hydrotreating, between 0 and 200 ppm, preferably between 0 and 50 ppm, even more preferably between 0 and 30 ppm. The sulfur content is preferably less than 1000 ppm, the asphaltene content is preferably 200 ppm, while the metal (Ni or V) content is less than 1 ppm.

[0099] The hydrocracking process according to the invention may include a fractionation step between the pretreatment of the feedstock and the hydrocracking reactor(s) using the catalyst according to the invention. In the preferred case where the hydrocracking process is carried out without fractionation (gas and liquid) between the pretreatment and the hydrocracking reactor(s) using the catalyst according to the invention, the nitrogen and sulfur removed from the liquid after the pretreatment are injected in the form of NH3 and H2S into the reactor(s) containing the catalyst according to the invention.

[0100] According to the present invention, the temperature during the process for hydrocracking the hydrocarbon feedstock according to the present invention is 200°C to 480°C, the total pressure during this is 1MPa to 25MPa, the ratio of the volume of hydrogen per volume of the hydrocarbon feedstock is 80 to 5000 liters / liter, and the hourly space velocity (HSV), defined by the ratio of the volumetric flow rate of the hydrocarbon feedstock per volume of the catalyst packed in the reactor, is 0.1 to 50 h -1 It is.

[0101] Preferably, the hydrocracking process according to the invention is carried out in the presence of hydrogen at a temperature between 250° C. and 480° C., preferably between 320° C. and 450° C., highly preferably between 330° C. and 435° C., under a pressure between 2 and 25 MPa, highly preferably between 3 and 20 MPa, for 0.1 to 20 h. -1 , preferably 0.1 to 6 hours -1 , preferably 0.2 to 3 hours -1 The amount of hydrogen introduced is set so that the volume ratio of hydrogen volume (liters) / hydrocarbon volume (liters) is 100 to 2000 L / L.

[0102] The process can be carried out in one or two steps depending on the targeted degree of conversion of the feedstock, with or without recycling the unconverted portion. The catalyst according to the invention can be used in a non-limiting manner in one or two steps of the hydrocracking process, alone or in combination with another hydrocracking catalyst.

[0103] The operating conditions used in the process according to the invention generally make it possible to obtain a conversion per pass of more than 15% by weight, and even more preferably between 20 and 100% by weight, to products having a boiling point below 340° C., and even better below 370° C.

[0104] The examples illustrate the invention but do not limit its scope.

[0105] (Example) Example 1 - Preparation of Comparative Catalyst A The preparation by shaping of the support for catalyst A is carried out by kneading-extrusion of 60% by weight of commercial zeolite Y (zeolite CBV712 from Zeolyst) and 10% by weight of commercial zeolite beta (zeolite CP814e from Zeolyst) in the presence of commercial boehmite (Pural SB3 from SASOL). The lattice parameter of zeolite Y is 24.35 Å, the SiO2 / Al2O3 molar ratio is 12 and the specific surface area, measured by nitrogen physisorption according to the BET method, is 850 m 2 / g, the SiO2 / Al2O3 molar ratio of zeolite beta is 25, and the specific surface area, measured by nitrogen physisorption according to the BET method, is 670 m 2 The extrudates obtained are dried at 80° C. and then calcined at 600° C. in moist air (5% by weight water per kg of dry air). The calcined support contains, on a dry basis, 60% by weight of zeolite Y, 10% by weight of zeolite beta and 30% by weight of alumina, i.e. a weight ratio of Y / Beta in the catalyst=6.

[0106] Catalyst A is prepared by dry impregnation of the resulting support with an aqueous solution containing the elements Ni, Mo. This solution is obtained by dissolving the following precursors in water: nickel nitrate and ammonium heptamolybdate. The amount of precursor in the solution is adjusted according to the targeted concentration on the final catalyst. After dry impregnation, the catalyst is dried in air at 120°C.

[0107] The weight percentages in the catalyst are, respectively, on a dry basis: molybdenum (in the form of MoO3) 15.1 wt. %, nickel (in the form of NiO) 3.3 wt. %.

[0108] Example 2 - Preparation of Comparative Catalyst B The preparation by shaping of the support for catalyst B is carried out by kneading-extrusion of 60% by weight of zeolite Y and 10% by weight of zeolite beta (zeolite CP814e from Zeolyst) in the presence of commercial boehmite (Pural SB3). The lattice parameter of zeolite Y is 24.42 Å, the SiO2 / Al2O3 molar ratio is 5.2 and the specific surface area, measured by nitrogen physisorption according to the BET method, is 800 m 2 / g, the SiO2 / Al2O3 molar ratio of zeolite beta is 25, and the specific surface area, measured by nitrogen physisorption according to the BET method, is 670 m 2The extrudates obtained are dried at 80° C. and then calcined at 600° C. in moist air (5% by weight water per kg of dry air). The calcined support contains, on a dry basis, 60% by weight of zeolite Y, 10% by weight of zeolite beta and 30% by weight of alumina, i.e. a weight ratio of Y / Beta in the catalyst=6.

[0109] Catalyst B is prepared by dry impregnation of the resulting support, using an aqueous solution containing the elements Ni, Mo. This solution is obtained by dissolving the following precursors in water: nickel nitrate and ammonium heptamolybdate. The amount of precursor in the solution is adjusted according to the targeted concentration on the final catalyst. After dry impregnation, the catalyst is dried in air at 120°C.

[0110] The weight percentages in the catalyst are, respectively, on a dry basis: molybdenum (in the form of MoO3) 15.1 wt. %, nickel (in the form of NiO) 3.3 wt. %.

[0111] Example 3 - Preparation of Comparative Catalyst C The preparation by shaping of the support for catalyst C is carried out by kneading-extrusion in the presence of 60% by weight of zeolite Y and 10% by weight of commercial zeolite beta (CP814e) in commercial boehmite (Pural SB3). The lattice parameter of zeolite Y is 24.54 Å, the SiO2 / Al2O3 molar ratio is 5.2 and the specific surface area, measured by nitrogen physisorption according to the BET method, is 830 m 2 / g, the SiO2 / Al2O3 molar ratio of zeolite beta is 25, and the specific surface area, measured by nitrogen physisorption according to the BET method, is 670 m 2 The extrudates obtained are dried at 80° C. and then calcined at 600° C. in moist air (5% by weight water per kg of dry air). The calcined support contains, on a dry basis, 60% by weight of zeolite Y, 10% by weight of zeolite beta and 30% by weight of alumina, i.e. a weight ratio of Y / Beta in the catalyst=6.

[0112] Catalyst C is prepared by dry impregnation of the resulting support, using an aqueous solution containing the elements Ni, Mo. This solution is obtained by dissolving the following precursors in water: nickel nitrate and ammonium heptamolybdate. The amount of precursor in the solution is adjusted according to the targeted concentration on the final catalyst. After dry impregnation, the catalyst is dried in air at 120°C.

[0113] The weight percentages in the catalyst are, respectively, on a dry basis: molybdenum (in the form of MoO3) 15.1 wt. %, nickel (in the form of NiO) 3.3 wt. %.

[0114] Example 4 - Preparation of Catalyst D in Accordance with the Invention The preparation by shaping of the support for catalyst D is carried out by kneading-extrusion in the presence of commercial boehmite (Pural SB3) with 63% by weight of zeolite Y and 3.5% by weight of zeolite beta (CP814e). The lattice parameter of zeolite Y is 24.54 Å, the SiO2 / Al2O3 molar ratio is 5.2 and the specific surface area is 830 m2, measured by nitrogen physisorption according to the BET method. 2 / g, the SiO2 / Al2O3 molar ratio of zeolite beta is 25, and the specific surface area, measured by nitrogen physisorption according to the BET method, is 670 m 2 / g. The extrudates obtained are dried at 80° C. and then calcined at 600° C. in moist air (5% by weight water per kg of dry air). The calcined support contains, on a dry basis, 63% by weight of zeolite Y, 3.5% by weight of zeolite beta and 30% by weight of alumina, i.e. a weight ratio of Y / Beta in the catalyst=18. After dry impregnation, the catalyst is dried in air at 120° C.

[0115] Catalyst D is prepared by dry impregnation of the resulting support with an aqueous solution containing the elements Ni, Mo. This solution is obtained by dissolving the following precursors in water: nickel nitrate and ammonium heptamolybdate. The amount of precursor in the solution is adjusted according to the targeted concentration on the final catalyst.

[0116] The weight percentages in the catalyst are as follows, respectively, on a dry basis: molybdenum (in the form of MoO3) 10 wt. %, nickel (in the form of NiO) 2.0 wt. %.

[0117] Example 5 The performance of the above catalysts is evaluated in a single step in the hydrocracking of feedstocks containing vacuum distillate fractions and gas oils using an isothermal test pilot unit in a downflow configuration.

[0118] The test feedstock undergoes hydrotreating (HDT). After the hydrotreating step, the density of the test feedstock at 15° C. is 0.8755 g / mL, the residual nitrogen content is 23 ppm by weight, and the residual sulfur content is 16 ppm by weight. The initial boiling point of the simulated distillation for the test feedstock after hydrotreating is 163.3° C., and the end point is at 578.7° C. The 50% point of the simulated distillation is at 391.7° C. To simulate the partial pressures of hydrogen sulfide and ammonia generated by the HDT step of the process, the test feedstock is spiked with DMDS and aniline, respectively, to obtain 8820 ppm by weight of sulfur and 1900 ppm by weight of nitrogen in the final spiked feedstock.

[0119] Each catalyst was evaluated separately and sulfided under straight run gas oil (SRGO) feed (i.e., gas oil feed derived from direct distillation of crude oil) with 4 wt.% dimethyl sulfide (DMDS) and 2 wt.% aniline added prior to hydrocracking testing. The HSV during sulfidation was 2h -1 (HSV=Hourly Space Velocity), the H2 / feed volume ratio is 1000 NL / L, the total pressure is 140 bar (i.e., 14.0 MPa), and the holding temperature is 350° C. for 6 hours.

[0120] After sulfurization, the operating conditions are adjusted to those used for the hydrocracking tests: HSV 1.5h -1, H2 / feed volume ratio of 1000 NL / L, total pressure of 140 bar (i.e., 14.0 MPa). The reactor temperature is adjusted to target a net conversion of 65 wt.% of the 216°C+ fraction after 150 hours from the feed.

[0121] Net conversion is defined as the yield of the cut (or fraction) boiling below 216°C minus the yield of the cut present in the test feedstock boiling below 216°C.

[0122] The performance of the catalysts is compared with that of catalyst B, considered as the reference, and is reported in Table 1. The relative activity in degrees Celsius (°C) is obtained from the difference between the temperature of reference catalyst B at which a net conversion of 65% is obtained and that obtained with the catalyst to be evaluated. The relative yield of the 68-216°C cut is determined in both cases as the difference between the yield of the catalyst to be evaluated and the yield of reference catalyst B obtained at a net conversion of 65 wt% of the 216°C+ cut. Positive values ​​result in improved performance, i.e. higher activity or higher yield.

[0123] [Table 1]

[0124] The results reported in the above table show that catalyst D according to the invention, having a combination of zeolite Y and zeolite Beta in a weight ratio of 18, with the lattice parameter of zeolite Y being 24.54 Å, makes it possible to obtain a gain in selectivity towards the naphtha fraction compared to comparative catalysts A, B and C, which use zeolite Y but with a lower lattice parameter and / or Y / Beta ratio.

[0125] Comparison of the performance of catalysts C and D clearly shows that increasing the lattice parameter of zeolite Y alone is not sufficient to obtain increased selectivity towards the naphtha fraction. This must be coupled with the use of zeolite Beta in a specific ratio compared to zeolite Y.

[0126] It is also observed that catalyst D (relative activity of D=0) has the additional advantage that the conversion activity is at least equal to catalysts A and B (relative activity of A=-9 and relative activity of B=0) at a lower total zeolite content (total zeolite content of catalyst D=63+3.5=66.5 wt.% vs. catalysts A and B: total zeolite content=60+10=70 wt.%).

Claims

1. A hydrocracking catalyst comprising at least one hydrodehydrogenating element and a support, the hydrodehydrogenating element being selected, alone or in mixture, from the group formed by the elements of group VIB and the non-noble metal elements of group VIII of the periodic table, the support comprising at least one porous mineral matrix, the initial lattice constant of the unit cell being a ０ 1. A hydrocracking catalyst comprising zeolite Y having a molecular weight of greater than 24.42 Å and zeolite beta, wherein the weight ratio of said zeolite Y to said zeolite beta in the catalyst is strictly greater than 12.

2. Catalyst according to claim 1, wherein the group VIII element is selected from iron, cobalt, nickel, preferably from nickel and cobalt, alone or in mixture, and the content of group VIII element is between 0.5% and 8% by weight of oxide, preferably between 0.5% and 6% by weight of oxide, highly preferably between 1.0% and 4% by weight of oxide, relative to the total weight of the catalyst.

3. Catalyst according to claim 1, wherein the Group VIB element is selected from tungsten and molybdenum, alone or in a mixture, and the content of Group VIB element is between 1% and 30% by weight of oxide, preferably between 2% and 25% by weight of oxide, highly preferably between 5% and 20% by weight of oxide, and even more preferably between 5% and 16% by weight of oxide, relative to the total weight of the catalyst.

4. The catalyst contains phosphorus, and the phosphorus content is, relative to the total weight of the catalyst, ２ O ５ 0.5% to 10% by weight of the oxide, preferably P ２ O ５ 1.0 wt% to 6 wt% by weight of the oxide, more preferably P ２ O ５ 10. The catalyst of claim 1, wherein the oxide is present in an amount of 1.0% to 4% by weight.

5. The initial lattice constant a of the unit cell of zeolite Y ０ is between 24.42 Å and 24.70 Å, preferably greater than 24.45 Å and less than 24.70 Å, preferably greater than 24.50 Å and less than 24.70 Å, preferably between 24.52 Å and 24.70 Å, preferably between 24.52 Å and 24.65 Å, preferably between 24.52 Å and 24.60 Å, and highly preferably between 24.52 Å and 24.58 Å.

6. Catalyst according to claim 1, wherein the zeolite Y content of the catalyst is between 26% and 79% by weight relative to the total weight of the catalyst.

7. Catalyst according to claim 1, wherein the zeolite beta content of the catalyst is between 1% and 6% by weight relative to the total weight of the catalyst.

8. Catalyst according to claim 1, wherein the content of at least one porous mineral matrix of said catalyst is between 7% and 47% by weight relative to the total weight of said catalyst.

9. Catalyst according to claim 1, wherein the weight ratio of said zeolite Y to said zeolite beta in the catalyst is from 13 to 40, preferably from 13 to 30, preferably from 14 to 20, even more preferably from 14 to 18.

10. 10. A process for hydrocracking at least one hydrocarbon feedstock in the presence of a catalyst according to any one of claims 1 to 9, wherein at least 50% by weight of the compounds of the feedstock have an initial boiling point above 300°C and a final boiling point below 650°C, the temperature during hydrocracking is between 200°C and 480°C, the total pressure is between 1 MPa and 25 MPa, the ratio of the volume of hydrogen per volume of hydrocarbon feedstock is between 80 and 5000 liters / liter, and the hourly space velocity (HSV), defined by the ratio of the volumetric flow rate of the hydrocarbon feedstock per volume of catalyst packed in the reactor, is between 0.1 and 50 h －１ That's the method.