Classifications

• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
  • C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
  • C10G49/04—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used containing nickel, cobalt, chromium, molybdenum, or tungsten metals, or compounds thereof
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
  • C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
  • C10G47/10—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
  • C10G47/12—Inorganic carriers
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
  • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
  • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
  • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J23/85—Chromium, molybdenum or tungsten
  • B01J23/88—Molybdenum
  • B01J23/883—Molybdenum and nickel
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/61—Surface area
  • B01J35/612—Surface area less than 10 m2/g
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/61—Surface area
  • B01J35/613—10-100 m2/g
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/61—Surface area
  • B01J35/615—100-500 m2/g
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/63—Pore volume
  • B01J35/633—Pore volume less than 0.5 ml/g
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/63—Pore volume
  • B01J35/635—0.5-1.0 ml/g
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
  • B01J35/63—Pore volume
  • B01J35/638—Pore volume more than 1.0 ml/g
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/0201—Impregnation
  • B01J37/0205—Impregnation in several steps
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/08—Heat treatment
  • B01J37/082—Decomposition and pyrolysis
  • B01J37/088—Decomposition of a metal salt
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
  • C07C5/22—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by isomerisation
  • C07C5/27—Rearrangement of carbon atoms in the hydrocarbon skeleton
  • C07C5/2767—Changing the number of side-chains
  • C07C5/277—Catalytic processes
  • C07C5/2791—Catalytic processes with metals
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C6/00—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions
  • C07C6/08—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond
  • C07C6/12—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring
  • C07C6/126—Preparation of hydrocarbons from hydrocarbons containing a different number of carbon atoms by redistribution reactions by conversion at a saturated carbon-to-carbon bond of exclusively hydrocarbons containing a six-membered aromatic ring of more than one hydrocarbon
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J35/00—Catalysts, in general, characterised by their form or physical properties
  • B01J35/50—Catalysts, in general, characterised by their form or physical properties characterised by their shape or configuration
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
  • C10G2400/30—Aromatics
• • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
  • Y02—TECHNOLOGIES OR APPLICATIONS FOR MITIGATION OR ADAPTATION AGAINST CLIMATE CHANGE
  • Y02P—CLIMATE CHANGE MITIGATION TECHNOLOGIES IN THE PRODUCTION OR PROCESSING OF GOODS
  • Y02P20/00—Technologies relating to chemical industry
  • Y02P20/50—Improvements relating to the production of bulk chemicals
  • Y02P20/52—Improvements relating to the production of bulk chemicals using catalysts, e.g. selective catalysts

Definitions

• the invention relates to the conversion of aromatics in the production of aromatics for the petrochemical industry (benzene, toluene, paraxylene, orthoxylene).
• the aromatic complex is supplied with charges C6 to C10 +, the aromatic alkyls are extracted there and then converted into desired intermediates.
• the products of interest are aromatics with 0, 1 or 2 methyls, xylenes having the highest market value. Methyl groups should therefore be available.
• a hydrodealkylation reaction is a dealkylation reaction (substitution, in a molecule, of a hydrogen atom for an alkyl radical) in which the removal of the alkyl group from aromatic molecules is carried out in the presence of hydrogen. Specifically, it is a terminal cut of the alkyl chain at the "raz" of the nucleus.
• the catalysis can be of the acid type, used in particular on alkyl chains with 2 or more carbons but very ineffective for methyls, or metallic, when it is desired in particular to convert the methyls.
• the conversion of methyls is used in particular for the reduction of the cutting point of gasolines for which all the molecules must lose carbons, or for the production of benzene for which the reaction is pushed to the maximum to preserve only the aromatic nucleus.
• a hydrogenolysis reaction is a chemical reaction by which a carbon-carbon or carbon-heteroatom covalent bond is broken down or lysed by the action of hydrogen.
• a hydrodealkylation reaction can therefore be considered as a hydrogenolysis reaction of the carbon-carbon bond between an alkyl and an aromatic nucleus.
• a hydrogenolysis reaction also relates to the carbon-carbon bonds internal to the alkyl group with 2 or more carbons.
• Hydrodealkylation units are known from the prior art, mainly used to produce high purity benzene from toluene.
• the LITOL and DETOL processes of McDermott (formerly CB&I) are examples of hydrodealkylation which can be either thermal or catalytic.
• Commercial hydrodealkylation units operate generally a metal catalysis which implies a hydrogenolysis type reaction.
• the term hydrodealkylation is therefore not exclusive and alkyls with 2 or more carbons also undergo hydrogenolysis there. This type of unit can be called the hydrogenolysis unit of alkyl aromatics.
• the units mentioned above are used either to produce benzene from heavier mono-aromatics (toluene, xylenes, etc.), or to reduce the cutting point of gasolines. No particular care is taken with the total quantity of methyls available after the conversion unit.
• US Patent 4,177,219 describes catalysts for the conversion of ethyl-aromatics to aromatic methyls. This patent details a processing route that converts ethyl aromatics to methyl aromatics. It details in its state of the art catalysts that can be used on the hydrogenolysis of methyl-aromatics or more to produce benzene, catalysts based on nickel or on more noble metals (ruthenium). Cobalt and chromium alloys are also cited. This patent proposes an alloyed catalyst based on a group VIII metal promoted by zinc on an alumina of at least 100 m 2 / g as catalyst of choice for the selective conversion of ethyl-aromatics to methyl-aromatics.
• a first object of the present description is to overcome the problems of the prior art and to carry out a selective hydrogenolysis of ethyl-aromatics making it possible in particular to decrease the hydrogenolysis of methyl-aromatics, to increase the levels methyl groups on the aromatics, to keep a maximum of aromatic cycles, and to limit side reactions on the products formed.
• the abovementioned objects, as well as other advantages, are obtained by a hydrogenolysis process in which a hydrocarbon feed comprising aromatic compounds having at least 8 carbon atoms is treated, by means of a supply of hydrogen and in the presence of a catalyst, in order to convert into alkyl groups C2 + alkyl chains of said aromatic compounds and produce a hydrogenolysis effluent enriched in aromatic compounds substituted in methyl,
• the catalyst comprises a support comprising at least one refractory oxide, and an active phase comprising nickel and molybdenum, in which:
• the nickel content is between 0.1 and 25% by weight relative to the total weight of the catalyst
• the molybdenum content is between 0.1 and 20% by weight relative to the total weight of the catalyst.
• the catalyst comprises a moly ratio of molybdenum to nickel (Mo / Ni) of between 0.2 and 0.9.
• the nickel content is between 0.2 and 15% by weight relative to the total weight of the catalyst
• the molybdenum content is between 0.2 and 18% by weight relative to the total weight of the catalyst.
• the catalyst comprises a molar ratio of molybdenum to nickel of between 0.5 and 0.9.
• the nickel content is between 0.5 and 10% by weight relative to the total weight of the catalyst
• the molybdenum content is between 0.4 and 15% by weight relative to the total weight of the catalyst.
• the catalyst comprises a moly ratio of molybdenum to nickel of between 0.4 and 0.9.
• the specific surface (BET) of the refractory oxide is between 1 m 2 / g and 250 m 2 / g.
• the pore volume (Vp) of the refractory oxide is between 0.1 and 2 cm 3 / g.
• the abovementioned objects, as well as other advantages, are obtained by a process for the production of xylenes integrating the process of hydrogenolysis according to the first aspect, in order to enrich aromatic streams comprising methyl groups which are sent all or part in an aromatic complex to produce xylenes.
• an aromatic complex is a processing unit (e.g. separation, purification, transformation (e.g. isomerization, transalkylation)) of aromatics.
• At least one hydrogenolysis process is integrated into an aromatic complex according to at least one of the following configurations:
• At least one hydrogenolysis process is used to pretreat a hydrocarbon feed upstream of the aromatic complex
• At least one hydrogenolysis process is used to treat at least one internal cut in the aromatic complex.
• a hydrogenolysis catalyst for the hydrogenolysis of a hydrocarbon feed comprising aromatic compounds having at least 8 carbon atoms, the catalyst comprising a support, comprising at least one refractory oxide, and an active phase comprising nickel and molybdenum, in which:
• the nickel content being between 0.1 and 25% by weight relative to the total weight of the catalyst
• the molybdenum content being between 0.1 and 20% by weight relative to the total weight of the catalyst
• the catalyst comprising a molybdenum molybdenum to nickel ratio of between 0.2 and 0.9.
• the nickel content is between 0.5 and 10% by weight relative to the total weight of the catalyst
• the molybdenum content is between 0.4 and 15% by weight relative to the total weight of the catalyst.
• the catalyst comprises a molar ratio of molybdenum to nickel of between 0.5 and 0.9.
• the specific surface (BET) of the refractory oxide is between 1 m 2 / g and 250 m 2 / g; and / or in which the pore volume (Vp) of the refractory oxide is between 0.1 and 2 cm 3 / g.
• the hydrogenolysis catalyst comprising a support, comprising at least one refractory oxide, and an active phase comprising nickel and molybdenum, in which:
• the nickel content being between 0.1 and 25% by weight relative to the total weight of the catalyst
• the molybdenum content being between 0.1 and 20% by weight relative to the total weight of the catalyst; and -
• the catalyst comprising a molybdenum molybdenum to nickel ratio of between 0.2 and 0.9.
• stage b) being carried out after stage a) or stages a) and b) being carried out together, preferably, stage a) is carried out before stage b);
• step c) at least one step of drying the catalyst precursor obtained at the end of step a) and / or of step b) is carried out, at a temperature below 250 ° C;
• step c) a step of reducing the catalyst precursor obtained at the end of step c) is carried out by bringing said catalyst precursor into contact with a reducing gas at a temperature between 350 and 450 ° C.
• the preparation process comprises the following steps:
• step a) at least one step of drying the catalyst precursor obtained at the end of step a) is carried out, at a temperature below 250 ° C;
• step b) a step of bringing the catalyst precursor obtained at the end of step ca) is carried out with at least one solution containing at least one molybdenum precursor, cb) at least one step of drying the precursor is carried out of catalyst obtained at the end of step b), at a temperature below 250 ° C;
• step cb) a step of reducing the catalyst precursor obtained at the end of step cb) is carried out by bringing said catalyst precursor into contact with a reducing gas at a temperature between 350 and 450 ° C.
• the preparation process comprises the following steps:
• a step of bringing the support into contact with at least one solution containing at least one nickel precursor and at least one molybdenum precursor is carried out, c) at least one step of drying the catalyst precursor obtained with from step ab), at a temperature below 250 ° C; d) a step of reducing the catalyst precursor obtained at the end of step c) is carried out by bringing said catalyst precursor into contact with a reducing gas at a temperature between 350 and 450 ° C.
• the nickel precursor is nickel carbonate.
• the catalyst precursor undergoes an additional heat treatment step at a temperature between 250 and 1000 ° C., directly after a drying step.
• paraxylene In petrochemicals, paraxylene is one of the intermediaries with the highest market value. Its production requires mono-aromatics substituted in methyl, it is mainly produced by disproportionation of toluene, isomerization of xylenes or transalkylation of toluene with tri- or tetra-methyl-benzenes. To maximize the production of paraxylene, it is useful to maximize the amount of methyl group available per aromatic ring.
• mono-aromatics substituted in methyls are directly recoverable, which is not the case for mono-aromatics containing little or no methyl (example: ethyl benzene, propyl benzene , methyl-ethylbenzene). It is therefore preferable to convert these mono-aromatics to substituted aromatics (e.g. only) in methyls.
• a hydrogenolysis unit capable of increasing the quantity of methyl groups on the aromatic nuclei, in particular to increase the production of paraxylene.
• the objective of the hydrogenolysis unit according to the present invention is to produce methyl groups in place of alkyl groups with more than two carbon atoms.
• the object of the invention is to improve the performance of the hydrogenolysis unit.
• bimetallic catalysts of the NiMo type can be selective for the hydrogenolysis of ethyl-aromatics, the conservation of methyl-aromatics, and the limitation of demethylation reactions on the products formed.
• group VIII according to the CAS classification corresponds to the metals in columns 8, 9 and 10 according to the new IUPAC classification.
• the specific surface of the catalyst or of the support used for the preparation of the catalyst according to the invention is understood to mean the BET specific surface determined by nitrogen adsorption in accordance with standard ASTM D 3663-78 established on the basis of the BRUNAUER-EMMETT method. -TELLER described in the periodical "The Journal of American Society", 60, 309, (1938).
• pore volume of the catalyst or of the support used for the preparation of the catalyst according to the invention is meant the volume measured by intrusion with a mercury porosimeter according to standard ASTM D4284-83 at a maximum pressure of 4000 bar (400 MPa), using a surface tension of 484 dyne / cm and a contact angle of 140 °.
• the wetting angle was taken equal to 140 ° following the recommendations of the book "Engineering techniques, treatise analysis and characterization", pages 1050-1055, written by Jean Charpin and Bernard Rasneur.
• the value of the pore volume corresponds to the value of the pore volume measured by intrusion with a mercury porosimeter measured on the sample minus the value of the pore volume measured by intrusion with a mercury porosimeter measured on the same sample for a pressure corresponding to 30 psi (about 0.2 MPa).
• the catalyst according to the invention comprises a bimetallic catalyst of the NiMo type and comprises a support comprising at least one refractory oxide, and an active phase.
• Said active phase is based on nickel, in particular to promote the terminal hydrogenolysis of the alkyl chains, and based on molybdenum, a metal which selects to limit the adsorption positions of aromatics on metal particles.
• the nickel content is between 0.1 and 25% by weight of said element relative to the total weight of the catalyst, preferably between 0.2 and 15%, and even more preferably between 0.5 and 10% by weight relative to the total weight of catalyst.
• the molybdenum content is between 0.1 and 20% by weight of said element relative to the total weight of the catalyst, preferably between 0.2 and 18% by weight, preferably between 0.4 and 15% by weight relative to the weight total catalyst.
• the catalyst comprises a molybdenum molybdenum to nickel ratio (Mo / Ni) of between 0.2 and 0.9 (mol / mol), preferably between 0.4 and 0.9, and even more preferably between 0, 5 and 0.9.
• Mo / Ni molybdenum molybdenum to nickel ratio
• the refractory oxide is crystalline or not, with structured porosity or not.
• the refractory oxide is selected from the metal oxides of groups 2, 3, 4, 13 and 14 of the new periodic classification of the elements IUPAC, such as for example the oxides of magnesium, of aluminum, silicon, titanium, zirconium, thorium, taken alone or as a mixture between them, or as a mixture with other metal oxides of the periodic table.
• the refractory oxide is inorganic.
• the refractory oxide is essentially neutral in terms of acidity basicity.
• the refractory oxide is chosen from low surface silicas (ie BET ⁇ 250 m 2 / g; eg with less than 100 ppm by weight of AI), titanium oxides, aluminas ( eg with less than 100 ppm by weight of Si), clays, coals.
• the refractory oxide is heat pretreated, optionally in the presence of water.
• the porous support is chosen from the group consisting of silica and alumina.
• the support is alumina.
• the refractory oxide is pretreated hydrothermally, for example to adjust its surface (in the sense of the BET surface) downward and its porous distributions upward.
• the specific surface (BET) of the refractory oxide is generally greater than 1 m 2 / g and less than 250 m 2 / g, for example between 2 and 200 m 2 / g, of preferably between 5 and 100 m 2 / g, preferably less than 100 m 2 / g, and even more preferably between 20 and 90 m 2 / g, such as substantially 80 m 2 / g.
• the pore volume (Vp) of the refractory oxide is between 0.1 and 2 cm 3 / g, preferably between 0.3 and 1.5 cm 3 / g, and even more preferably between 0.9 and 1.1 cm 3 / g, such that substantially 1.0 cm 3 / g.
• the refractory oxide may further comprise impurities (e.g. Ca, K, P, Mg, Fe, Si, Ti, W). According to one or more embodiments, the refractory oxide comprises less than 500 ppm by weight of impurities, preferably less than 200 ppm by weight of impurities, and even more preferably less than 100 ppm by weight of impurities relative to the total weight refractory oxide.
• impurities e.g. Ca, K, P, Mg, Fe, Si, Ti, W.
• the catalyst can also comprise at least one basic compound to limit reactions of an acidic nature (dealkylation of isopropylbenzene for example).
• the at least one basic compound is chosen from the group consisting of Na, K, Li, Ca.
• the content of basic compound is between 1 and 3% weight, preferably between 1 and 2% by weight, of said basic compound relative to the total weight of the catalyst.
• the catalyst is generally presented in all the forms known to those skilled in the art, for example in the form of balls (generally having a diameter between 1 and 8 mm), extrudates, tablets, hollow cylinders.
• the catalyst consists of extrudates with an average diameter generally between 0.5 and 10 mm, preferably between 0.8 and 3.2 mm and very preferably between 1, 0 and 2 , 5 mm and optionally of average length between 0.5 and 20 mm.
• the term “mean diameter” of the extrudates means the mean diameter of the circle circumscribed in the cross section of these extrudates.
• the catalyst can advantageously be presented in the form of cylindrical, multilobed, trilobed or quadrilobed extrudates. Preferably its shape will be three-lobed or four-lobed. The shape of the lobes can be adjusted according to all the methods known from the prior art.
• the process for preparing the bimetallic catalyst comprises the following stages:
• stage b) being carried out after stage a) or stages a) and b) being carried out together, preferably, stage a) is carried out before stage b);
• step c) at least one step of drying the catalyst precursor obtained at the end of step a) and / or of step b) is carried out, at a temperature below 250 ° C;
• step c) a step of reducing the catalyst precursor obtained at the end of step c) is carried out by bringing said catalyst precursor into contact with a reducing gas at a temperature between 350 and 450 ° C.
• the process for preparing the bimetallic catalyst comprises the following steps:
• step a) at least one step of drying the catalyst precursor obtained at the end of step a) is carried out, at a temperature below 250 ° C;
• step b) a step of bringing the catalyst precursor obtained at the end of step ca) is carried out with at least one solution containing at least one molybdenum precursor, cb) at least one step of drying the precursor is carried out of catalyst obtained at the end of step b), at a temperature below 250 ° C;
• step cb) a step of reducing the catalyst precursor obtained at the end of step cb) is carried out by bringing said catalyst precursor into contact with a reducing gas at a temperature between 350 and 450 ° C.
• the process for preparing the bimetallic catalyst comprises the following steps:
• a step of bringing the support into contact with at least one solution containing at least one nickel precursor and at least one molybdenum precursor is carried out, c) at least one step of drying the catalyst precursor obtained with from step ab), at a temperature below 250 ° C;
• step c) a step of reducing the catalyst precursor obtained at the end of step c) is carried out by bringing said catalyst precursor into contact with a reducing gas at a temperature between 350 and 450 ° C.
• Step a) Contacting the nickel precursor
• step a The deposition of nickel on said support, in accordance with the implementation of step a), can be carried out by impregnation, dry or in excess, or even by deposition - precipitation, according to methods well known to those skilled in the art. job.
• Said step a) is preferably carried out by impregnating the support, for example by bringing said support into contact with at least one aqueous and / or organic solution (for example with at least one organic solvent, such as methanol and / or ethanol and / or phenol and / or acetone and / or toluene and / or dimethyl sulfoxide).
• at least one organic solvent for example with at least one organic solvent, such as methanol and / or ethanol and / or phenol and / or acetone and / or toluene and / or dimethyl sulfoxide.
• the organic solvent is vaporizable during the heat treatment stages.
• the solution contains at least one nickel precursor at least partially in the dissolved state.
• the contacting of said support is carried out with at least one colloidal solution of at least one precursor of nickel, in oxidized form (nanoparticles of oxide, of oxy (hydroxide) or of hydroxide nickel) or in reduced form (metallic nanoparticles of nickel in the reduced state).
• the solution is aqueous.
• the pH of the aqueous solution is modified by the addition of an acid or a base, preferably by the addition of a base.
• the pH of the aqueous solution is greater than 1 1, preferably between 1 1 and 13, even more preferably between 1 1 and 12, such as substantially 1 1, 5.
• the aqueous solution contains ammonia or ammonium ions NH 4 + .
• the aqueous solution may be an aqueous ammonia solution, with optionally a buffer solution for regulating a pH during the impregnation phase which is constant (eg use of an ammonium carbonate salt).
• the pH of the aqueous solution is adjusted by means of a mixture of ammonia (NH 3 ) and ammonium carbonate (NH 4 ) 2 C0 3 .
• said step a) is carried out by dry impregnation, which comprises bringing the catalyst support into contact with a solution, containing at least one nickel precursor, the volume of the solution of which is between 0.75 and 1.25 times, preferably between 0.8 and 1.2 times, preferably between 0.9 and 1.1 times, even more preferably between 0.95 and 1.05 times, the pore volume of the support to be impregnated.
• the nickel precursor when introduced in aqueous solution, the latter is in the form of carbonate, acetate, chloride, hydroxide, hydroxycarbonate, oxalate, sulfate, formate, nitrate, complexes formed by a polyacid or an acid-alcohol and its salts, complexes formed with acetylacetonates, tetrammine or hexammine complexes, or even any other inorganic derivative soluble in aqueous solution.
• nickel precursor nickel carbonate, nickel hydroxide, nickel chloride, nickel hydroxycarbonate, and / or nickel nitrate.
• the nickel precursor is nickel carbonate.
• the nickel precursor is ammonium nickel carbonate (e.g. nickel carbonate + ammonia).
• a particular effect of nickel carbonate, and in particular of ammoniacal nickel carbonate, used as a precursor is that it allows better decomposition at low temperature favoring the dispersion of the active phase.
• step b The deposition of molybdenum on said support, in accordance with the implementation of step b), can be carried out by impregnation, dry or in excess, or even by deposition - precipitation, according to methods well known to those skilled in the art. job.
• Said step b) is preferably carried out by impregnating the support, for example by bringing said support into contact with at least one aqueous and / or organic solution (for example with a solution comprising methanol and / or ethanol and / or phenol and / or acetone and / or toluene and / or dimethyl sulfoxide).
• the organic solvent is vaporizable during the heat treatment stages.
• the solution contains at least one molybdenum precursor at least partially in the dissolved state.
• the solution is aqueous.
• the pH of the aqueous solution is modified by the addition of an acid or a base, preferably by the addition of a base.
• the pH of the aqueous solution is greater than 1 1, preferably between 1 1 and 13, even more preferably between 1 1 and 12, such as substantially 1 1, 5.
• the aqueous solution contains ammonia or ammonium ions NH 4 + .
• the aqueous solution can be an aqueous ammonia solution, with optionally a solution buffer to regulate a pH during the impregnation phase which is constant (eg use of an ammonium carbonate salt).
• the pH of the aqueous solution is adjusted by means of a mixture of ammonia (NH 3 ) and ammonium carbonate (NH 4 ) 2 C0 3 .
• said step b) is carried out by dry impregnation, which comprises bringing the catalyst support into contact with a solution, containing at least one molybdenum precursor, the volume of the solution of which is between 0.75 and 1.25 times, preferably between 0.8 and 1.2 times, preferably between 0.9 and 1.1 times, even more preferably between 0.95 and 1.05 times, the pore volume of the support to be impregnated.
• a molybdenum precursor is preferably used in mineral or organic form.
• the molybdenum precursor in mineral form, can be chosen from ammonium heptamolybdate, or any other precursor obtained by dissolving Mo0 3 in a mineral and organic acid or any other heteropoly anion containing Molybdenum, or phosphomolybtic precursors (eg H 3 RMqi 2 0 4 o).
• the molybdenum precursor in organic form, can be chosen from the organometallic complexes obtained by reaction between an oxide or a sulfide of molybdenum and a fatty acid.
• the molybdenum precursor comprises ammonium heptamolybdate.
• Steps a) and b) can be carried out together.
• the impregnation of the nickel precursor is carried out before the impregnation of the molybdenum precursor, so as to avoid the formation of catalytic sites where the nickel atoms are too exposed, which is less desirable in the context of the present invention. as this can lead to poorer activity and / or selectivity.
• Stage c) of drying the catalyst precursor obtained at the end of stage a) and stage b) is carried out at a temperature below 250 ° C., preferably between 15 and 240 ° C., more preferably between 30 and 220 ° C, even more preferably between 50 and 200 ° C, and even more preferably between 70 and 180 ° C (eg at substantially 150 ° C), for a period typically between 5 minutes and 24 hours (eg for approximately 30 minutes). Longer durations are not excluded, but do not necessarily bring improvement.
• the drying step can be carried out by any technique known to those skilled in the art. It is advantageously carried out under an inert atmosphere or under an atmosphere containing oxygen or under a mixture of inert gas and oxygen. It is advantageously carried out at atmospheric pressure or at reduced pressure. Preferably, this step is carried out at atmospheric pressure and in the presence of air and / or nitrogen.
• the drying step comprises a first maturation period (gentle drying), then a second evaporation period (strong drying) carried out between 30 and 220 ° C.
• the maturing step is carried out at a temperature below 30 ° C (e.g. at room temperature), for a duration typically between 5 minutes and 24 hours (e.g. overnight).
• the dried catalyst precursor can undergo an additional heat treatment step at a temperature between 250 and 1000 ° C and preferably between 250 and 750 ° C, preferably between 250 and 500 ° C (eg at a temperature of approximately 280 ° C), for a period typically between 5 minutes and 10 hours (eg for approximately 45 minutes), under an inert atmosphere or under an oxygen-containing atmosphere, in the presence of water or not. Longer treatment times are not excluded, but do not bring about any improvement.
• Heat treatment is understood to mean temperature treatment respectively without the presence or presence of water. In the latter case, contact with water vapor can take place at atmospheric pressure or at autogenous pressure. Several combined cycles without the presence or presence of water can be performed.
• the process for preparing the bimetallic catalyst comprises a heat treatment step after each drying step c).
• the heat treatment is a calcination (heat treatment in the presence of oxygen), optionally in the presence of water.
• the catalyst precursor comprises nickel in the form of oxide, that is to say in the form of NiO and also in the form of mixed oxide NiOMo allowing the creation of alloys after reduction step.
• a reducing treatment step d) is carried out in the presence of a reducing gas so as to obtain a catalyst comprising nickel with less partially in metallic form.
• This step can be carried out ex-situ or in-situ.
• This treatment makes it possible to activate said catalyst and to form metallic particles, in particular nickel in the zero-value state.
• the in-situ implementation that is to say after the loading of the catalyst into a hydrogenolysis reactor
• the reducing treatment of the catalyst makes it possible to dispense with an additional and optional step of passivation of the catalyst by an oxygenated compound.
• the reducing gas is preferably hydrogen.
• Hydrogen can be used pure or as a mixture (for example a hydrogen / nitrogen, hydrogen / argon, hydrogen / methane mixture). In the case where hydrogen is used as a mixture, all the proportions are possible.
• said reducing treatment is carried out at a temperature between 350 and 450 ° C, preferably between 370 and 430 ° C, even more preferably between 390 and 410 ° C (eg at a temperature of approximately 400 ° C).
• the duration of the reducing treatment is between 5 minutes and 48 hours, preferably between 30 minutes and 36 hours, more preferably between 1 and 24 hours, and even more preferably between 2 and 20 hours (eg a duration of approximately 16h).
• the rise in temperature to the desired reduction temperature is slow, for example fixed between 0.1 and 10 ° C / min, preferably between 0.3 and 7 ° C / min.
• the catalyst prepared according to the process according to the invention can optionally undergo a passivation step with an oxygenated, sulfur-containing compound or with C0 2 , which makes it possible to improve the selectivity of the catalysts, to avoid thermal runaway during catalyst starts. new (“run away” according to Anglo-Saxon terminology), and reduce the formation of coke and / or organic deposits on the catalyst.
• a passivation step is for example useful following the reduction step when the latter is carried out ex-situ.
• the present invention also relates to a hydrogenolysis process, using a catalyst according to the invention or a catalyst prepared by the preparation process according to the invention, for treating a hydrocarbon feed rich in aromatic compounds having at least 8 carbon atoms and transform one or more alkyl group (s) with at least two carbon atoms (ethyl, propyl, butyl, isopropyl groups, etc.) attached to a benzene ring, into one or more group (s) ) methyl (s), that is to say formed from a single CH 3 group.
• a catalyst according to the invention or a catalyst prepared by the preparation process according to the invention for treating a hydrocarbon feed rich in aromatic compounds having at least 8 carbon atoms and transform one or more alkyl group (s) with at least two carbon atoms (ethyl, propyl, butyl, isopropyl groups, etc.) attached to a benzene ring, into one or more group (s) ) methyl (s), that is to say formed
• the hydrogenolysis process according to the invention makes it possible to treat the hydrocarbon feedstock, by means of a supply of hydrogen, and in the presence of the catalyst according to the invention, to convert into alkyl groups C2 + alkyl chains of aromatic compounds; and produce a hydrogenolysis effluent enriched in aromatic compounds substituted in methyl with respect to the hydrocarbon feed.
• the hydrogenolysis reaction is carried out with the following operating conditions:
• - PPH between 0.1 and 50 h 1 , preferably between 0.5 and 30 h 1 , and more preferably between 1 and 20 h 1 (eg between 1 and 7 h 1 ).
• PPH corresponds to the weight of hourly hydrocarbon feedstock injected relative to the weight of loaded catalyst.
• the hydrogenolysis process is carried out in a hydrogenolysis reactor of the fixed bed or moving bed type.
• a moving bed can be defined as a gravity flow bed, such as those encountered in the catalytic reforming of gasolines.
• the method comprises treating the hydrogenolysis effluent by means of a separation unit to produce a plurality of sections of liquid effluents.
• the hydrocarbon feedstock is mixed with the supply of hydrogen to the hydrogenolysis reactor and / or (e.g. directly) upstream of the hydrogenolysis reactor to form a feedstock mixture.
• the hydrogenolysis process further comprises heating the hydrocarbon feedstock or the feedstock mixture in a heating unit (e.g. directly) upstream of the hydrogenolysis reactor.
• the heating unit is adapted to be used under the following operating conditions: inlet temperature between 25 ° C and 400 ° C; and / or outlet temperature between 300 ° C and 550 ° C.
• the heating effluent from the heating unit is sent (e.g. directly) to the hydrogenolysis reactor.
• the hydrogenolysis effluent is sent (eg directly) to a cooling unit (eg heat exchanger) to form a cooled hydrogenolysis effluent.
• the cooling unit can be preceded by an effluent heat recovery equipment used to preheat the hydrocarbon charge or the charge mixture (eg upstream of the heating unit).
• the cooling unit is adapted to be used under the following operating conditions: inlet temperature between 100 ° C and 550 ° C; and / or outlet temperature between 25 ° C and 400 ° C.
• the cooled hydrogenolysis effluent is sent (e.g. directly) to a cooled effluent separation unit to produce a gaseous effluent comprising hydrogen and a liquid effluent.
• the gaseous effluent is sent to a recycling unit suitable for: compressing and / or purifying the gaseous effluent; optionally extracting a purge gas (e.g. methane) from the gaseous effluent; and / or mixing the gaseous effluent with the supply of hydrogen to form a mixture of hydrogen sent to the hydrogenolysis reactor and / or (e.g. directly) mixed with the hydrocarbon feedstock to form the mixture of depleted effluent.
• a purge gas e.g. methane
• the liquid effluent is sent to the separation unit to produce the plurality of sections of liquid effluents.
• the hydrocarbon feedstock comprises at least 90% by weight, preferably at least 95% by weight, more preferably at least 98% by weight (eg at least 99% by weight), of aromatic compounds (eg aromatic comprising minus 8 carbon atoms, such as aromatics comprising from 8 to 10 carbon atoms) relative to the total weight of the filler.
• aromatic compounds eg aromatic comprising minus 8 carbon atoms, such as aromatics comprising from 8 to 10 carbon atoms
• the aromatic compounds of the hydrocarbon feedstock comprise at least 50% by weight, preferably at least 70% by weight, more preferably at least 90% by weight (eg at least 95% by weight), of aromatic compounds comprising at least 9 carbon atoms, based on the total weight of the aromatic compounds in the hydrocarbon charge.
• the hydrocarbon feedstock comprises at least 90% by weight, preferably at least 95% by weight, more preferably at least 98% by weight (eg at least 99% by weight), of aromatic compounds comprising 9 carbon atoms relative to the total weight of the load.
• the hydrocarbon charge comprises at least 90% by weight of aromatic molecules having between 8 and 10 carbon atoms relative to the total weight of the hydrocarbon charge.
• the hydrocarbon feedstock comprises at least one internal flow of an aromatic complex for the production of paraxylene and / or the hydrogenolysis effluent is a feedstock sent to an aromatic complex for the production of paraxylene.
• the hydrocarbon charge comprises at least 90% by weight of aromatic molecules having 8 carbon atoms relative to the total weight of said charge.
• the hydrocarbon feedstock comprises a paraxylene extraction raffinate.
• the paraxylene extraction raffinate comprises (e.g. essentially) orthoxylene, metaxylene and ethylbenzene.
• the paraxylene extraction raffinate comprises (e.g. essentially) metaxylene and ethylbenzene.
• the hydrocarbon charge comprises at least 90% by weight of aromatic molecules having 9 carbon atoms relative to the total weight of said charge.
• the hydrocarbon feedstock comprises methyl-ethyl-benzenes and optionally tri-methyl-benzenes, preferably little or no tri-methyl-benzenes.
• the hydrocarbon charge comprises at least 90% by weight of aromatic molecules having 10 carbon atoms relative to the total weight of the hydrocarbon charge.
• the hydrocarbon feedstock 2 comprises tetra-methyl-benzenes and / or di-methyl-ethyl-benzenes and / or methyl-propyl-benzenes, preferably little or no tetra-methyl-benzenes .
• the hydrocarbon feedstock comprises less than 1000 ppm by weight, preferably less than 700 ppm by weight, more preferably less than 500 ppm by weight, even more preferably less than 300 ppm by weight, of water relative to the total weight of the load. Integration into an aromatic complex
• the hydrogenolysis process is integrated into a process for producing xylenes using an aromatic complex.
• the aromatic complex is supplied with hydrocarbon cuts mainly containing molecules whose carbon number ranges from 6 to 10.
• the hydrogenolysis process is used to pretreat a hydrocarbon feed upstream of the aromatic complex.
• external flows can directly feed the hydrogenolysis reactor (example reformate from 6 to 10 carbons, cut A9 / A10, etc.), and the effluents from the hydrogenolysis reactor are then directed to the aromatic complex .
• One or more hydrogenolysis processes is used to treat one or more sections internal to the aromatic complex.
• the hydrogenolysis reactor can be partially or totally supplied by one or more streams coming from units (e.g. fractionation / distillation columns, simulated moving bed) of the aromatic complex.
• the effluents from the hydrogenolysis reactor are then also returned to the aromatic complex.
• the effluents are then enriched in aromatics comprising methyl groups which are sent all or part of the aromatic complex in order to produce xylenes and optionally benzene.
• the support is in the form of extrudates (diameter of the extrusion die 1.6 mm) multi-lobed (three-lobed or four-lobed).
• Catalyst A non-compliant
• Catalyst A is prepared, first of all by dry impregnation of the metal salts (carbonates in our case), diluted in a solvent vaporizable at the heat treatment stages, (for example in our case water or an aqueous solution d ammonia), possibly with a buffer solution to regulate a pH during the impregnation phase which is constant (for example in the present case, ammonium carbonate is used).
• a solvent vaporizable for example in our case water or an aqueous solution d ammonia
• a buffer solution to regulate a pH during the impregnation phase which is constant for example in the present case, ammonium carbonate is used.
• the FX analysis of catalyst A gives an Ni content of 10% by weight, relative to the total weight of the catalyst.
• Catalyst B3 is produced from catalyst A by adding a second dry impregnation of Mo (in the form of ammonium heptamolybdate in the ammoniacal phase). Maturation is carried out by leaving the catalyst in the ambient overnight. The dry-impregnated catalyst is then dried at 150 ° C for 30 min and then calcined at 280 ° C for at least 45 minutes in dry air.
• the operating conditions for the hydrogenolysis step are as follows:
• the amount of catalyst loaded is 0.016 g.
• the charge used is a reformate bottom with the following composition (Table 1):
• TMB defines the sum of the 3 isomers of trimethylbenzene, and by MET the sum of the 3 methyl-ethylbenzene.
• the performance of the catalyst is characterized by the following performance indicators:
• methyl out / methyl in indicator is a base 100 indicator, which depends on the charge and the methyl level with respect to a given methyl creation target.
• the catalyst performance indicators are as follows (Table 2):
• NiMo type catalyst according to the invention is more selective for the relative conversion of TMB to iso conversion of MET. Indeed, we keep more TMB and the methyl level is increasing. In addition, a significantly improved selectivity with respect to toluene is observed (ie, the toluene produced from the reaction is less reactive). In the case of B2 we also observe a selectivity by particularly increased compared to benzene. The conservation rate of aromatic rings is also improved (ie, more limited aromatic hydrogenation rate).
• the increase in the Mo / Ni ratio to 0.90 gives a catalyst keeping an improved selectivity with respect to the conversion of TMB.
• the catalyst exhibits an increase in the hydrogenating activity on the aromatic cycles which limits the increase in the Mo / Ni ratio - this is particularly seen on B2 which has a higher hydrodealkylation.
• the high Mo / Ni ratio of 0.90 also exhibits improved selectivity with regard to successive reactions.
• the drop in the Mo / Ni ratio to 0.20 or even 0.10 shows that the selectivity of the catalyst with respect to the conversion of TMB is lost.
• the NiMo type catalyst according to the invention is particularly suitable for the conservation of TMB and the limitation of loss in the aromatic cycle.
• the NiMo catalyst according to the invention also makes it possible to limit the successive demethylation reactions.
• the term “understand” is synonymous with (means the same as) “include” and “contain”, and is inclusive or open and does not exclude other unreported material. It is understood that the term “understand” includes the exclusive and closed term “consist”. Furthermore, in the present description, the terms “approximately”, “substantially” “substantially”, “essentially”, “only” and “approximately” are synonymous with (mean the same as) lower and / or higher margin 10%, preferably 5%, very preferably 1%, of the given value.
• a composition comprising essentially or only a compound A corresponds to a composition comprising at least 90%, preferably at least 95%, very preferably at least 99%, of compound A.
• a duration of substantially 100 min corresponds to a duration of between 90 and 110 min, preferably between 95 and 105 min, very preferably between 99 and 101 minutes.

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• 2018
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