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
  • 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
  • C10G47/16—Crystalline alumino-silicate carriers
  • C10G47/20—Crystalline alumino-silicate carriers the catalyst containing other metals or compounds thereof
• • 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
  • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
  • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
  • B01J21/04—Alumina
• • 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
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
  • B01J29/084—Y-type faujasite
• • 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
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
  • B01J29/16—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J29/166—Y-type faujasite
• • 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
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/70—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65
  • B01J29/78—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of types characterised by their specific structure not provided for in groups B01J29/08 - B01J29/65 containing arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
  • B01J29/7815—Zeolite Beta
• • 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
  • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
  • B01J37/0027—Powdering
  • B01J37/0045—Drying a slurry, e.g. spray drying
• • 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
  • B01J37/03—Precipitation; Co-precipitation
  • B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
• • 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
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01F—COMPOUNDS OF THE METALS BERYLLIUM, MAGNESIUM, ALUMINIUM, CALCIUM, STRONTIUM, BARIUM, RADIUM, THORIUM, OR OF THE RARE-EARTH METALS
  • C01F7/00—Compounds of aluminium
  • C01F7/02—Aluminium oxide; Aluminium hydroxide; Aluminates
  • C01F7/04—Preparation of alkali metal aluminates; Aluminium oxide or hydroxide therefrom
  • C01F7/14—Aluminium oxide or hydroxide from alkali metal aluminates
  • C01F7/141—Aluminium oxide or hydroxide from alkali metal aluminates from aqueous aluminate solutions by neutralisation with an acidic agent
• • 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
  • C10G47/16—Crystalline alumino-silicate 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
  • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
  • B01J2229/10—After treatment, characterised by the effect to be obtained
  • B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
• • 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
  • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
  • B01J2229/30—After treatment, characterised by the means used
  • B01J2229/42—Addition of matrix or binder particles
• • 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
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/1074—Vacuum distillates

Definitions

• the present invention relates to the use in a hydrocracking process of a hydrocarbon feedstock of which at least 50% by weight of the compounds have an initial boiling point greater than 340 ° C. and an end boiling point. less than 540% of a catalyst comprising at least one Group VIB metal and / or at least one Group VIII metal of the Periodic Table and a support comprising at least one zeolite having at least one series of channels the opening of which is defined by a ring of 12 oxygen atoms (12MR), and at least one binder comprising at least one amorphous mesoporous alumina having a specific porous distribution said alumina having a very high connectivity with respect to the aluminas of the prior art.
• Said amorphous mesoporous alumina is advantageously shaped from an alumina gel having a high dispersibility, said alumina gel being itself obtained by precipitation of at least one aluminum salt according to a specific process.
• the hydrocracking catalysts used in the hydrocracking processes are all of the bifunctional type associating an acid function with a hydrogenating function.
• the acid function is provided by supports whose surfaces generally vary from 150
• Catalysts comprising, for example, zeolite Y of FAU structural type, or catalysts comprising, for example, a beta-type zeolite, have in turn a higher catalytic activity than silica-aluminas, but have selectivities in middle distillates (jet fuels and gas oils) lower. This difference is attributed to the difference in strength of acid sites on both types of materials.
• the Applicant has discovered that the use in a hydrocracking process of the hydrocarbon feedstock of a catalyst comprising at least one Group VIB metal and / or at least one Group VIII metal of the Periodic Table and a carrier comprising at least one minus a zeolite having at least one series of channels whose opening is defined by a ring of 12 oxygen atoms (12MR), and at least one binder comprising at least one amorphous mesoporous alumina prepared from a specific preparation process making it possible to obtain a highly dispersible alumina gel made it possible to improve the middle distillate selectivity while preserving or improving the catalytic activity of said zeolite catalysts, by relative to hydrocracking catalysts of the prior art.
• a binder comprising at least said specific alumina having a high connectivity by its preparation method, avoids overcracking of the treated feedstock and thus limit the production of light products not included in the average distillate pool.
• the subject of the present invention is a process for the hydrocracking of at least one hydrocarbon feedstock of which at least 50% by weight of the compounds have an initial boiling point of greater than 300 ° C. and a final boiling point of less than 540 ° C. at a temperature of between 200 ° and 480 ° C., at a total pressure e of between 1 MPa and 25 MPa with a ratio of volume of hydrogen per volume of hydrocarbon feedstock of between 80 and 5000 liters per liter and at a fixed hourly volume velocity (VVH) defined by the ratio of the volume flow rate of the liquid hydrocarbon feedstock by the volume of catalyst charged to the reactor of between 0.1 and 50 h -1 , said process using at least one catalyst comprising at least one Group VIB metal and / or at least one Group VIII metal of the Periodic Table and a support comprising at least one zeolite having at least one series of channels whose opening is defined by a ring of 12 oxygen atoms (12M R), and at least one binder comprising at least one
• step d) a step of drying the alumina gel obtained at the end of step c) to obtain a powder
• step f) a step of calcination of the raw material obtained at the end of step e) at a temperature of between 500 and 1000 °, with or without a flow of air containing up to 60% by volume of 'water.
• the alumina gel at the origin of the alumina used as binder in the catalyst support, is prepared from a precipitation stage in which at least 40% by weight of alumina with respect to the total amount of alumina formed at the end of said process for preparing the gel are formed as of the first precipitation step.
• This method is achieved through the implementation of a hydrothermal treatment step and in particular a ripening step to obtain a support having improved filterability, and facilitating its shaping.
• the connectivity of the alumina used as binder of the catalyst used in the process according to the invention is representative of the totality of the porosity of the alumina and in particular of the totality of the mesoporosity of the alumina, that is to say all the pores having an average diameter of between 2 and 50 nm.
• Connectivity is a relative quantity measured according to the procedure described in the Seaton publication (Liu H., Zhang L., Seaton N.A., Chemical Engineering Science, 47, 17-18, pp.4393-4404, 1992). This is a Monte Carlo simulation from nitrogen adsorption / desorption isotherms. These connectivity parameters are based on the theory of percolation. The connectivity is related to the numbers of adjacent pores and represents an advantage for the diffusion during the catalytic reactions of the molecules to be treated.
• the dispersibility index is defined as the weight of peptised alumina gel that can be dispersed by centrifugation in a polypropylene tube at 3600 G for 10 min.
• the invention relates to a process for hydrotreating at least a hydrocarbon feedstock including at least 50% by weight of the compounds have an initial boiling point above 340 ⁇ and a final boiling point below 540 ⁇ C.
• the charge may optionally contain asphaltenes.
• the asphaltene content is generally less than 3000 ppm by weight, preferably less than 1000 ppm by weight, more preferably less than 200 ppm by weight.
• the process for hydrocracking said hydrocarbon feedstock according to the invention is carried out at a temperature of between 200 and 480%, at a total pressure of between 1 MPa and 25 MPa with a volume ratio of hydrogen per volume of hydrocarbon feedstock of between 80 and 5000 liters per liter and at a Hourly Volumetric Rate (VVH) defined by the ratio of the volume flow rate of the liquid hydrocarbon feedstock to the volume of catalyst charged to the reactor of between 0.1 and 50 hrs "1 .
• VVH Hourly Volumetric Rate
• nickel-niobium-molybdenum, cobalt-niobium-molybdenum, nickel-niobium-tungsten, cobalt-niobium-tungsten the preferred combinations being: nickel-niobium-molybdenum, cobalt -niobium-molybdenum.
• nickel-cobalt-niobium-molybdenum the catalyst may also advantageously contain:
• the mixture in the aqueous reaction medium of at least one basic precursor and at least one acidic precursor requires either that at least the basic precursor or the acidic precursor comprises aluminum, or that the two precursors basic and acidic include aluminum.
• the aqueous reaction medium is water.
• said step a) is carried out in the absence of organic additive.
• the acidic and basic precursors, whether they contain aluminum or not, are mixed, preferably in solution, in the aqueous reaction medium, in such proportions that the pH of the resulting suspension is between 8.5 and 10. 5.
• the base / acid mass ratios are established by a curve of neutralization of the base by the acid.
• a curve is easily obtained by those skilled in the art.
• said precipitation step a) is carried out at a pH of between 8.5 and 10 and very preferably between 8.7 and 9.9.
• the flow rate of the acid-containing and / or basic precursor (s) containing aluminum depends on the size of the reactor used and thus on the quantity of water added to the reaction medium.
• said precipitation step a) is carried out at a temperature of between 10 and 45%, preferably between 15 and 40, more preferably between 20 and 45% and very preferably between 20 and 40 ° C.
• said precipitation step a) is carried out for a period of between 5 and 20 minutes, and preferably of 5 to 15 minutes.
• said preparation process comprises a hydrothermal treatment step b) of the suspension obtained at the end of the precipitation step a), said hydrothermal treatment step operating at a temperature of between 60 and 200 ° during a duration of between 30 minutes and 5 hours.
• said hydrothermal treatment step b) is carried out for a duration of between 40 minutes and 5 hours, preferably between 40 minutes and 3 hours, and preferably between 45 minutes and 2 hours.
• second optional precipitation step is carried out for a duration of between 40 minutes and 5 hours, preferably between 40 minutes and 3 hours, and preferably between 45 minutes and 2 hours.
• said preparation method preferably comprises a second precipitation step. Said second precipitation step makes it possible to increase the proportion of alumina produced.
• a heating step of the suspension obtained at the end of the precipitation step a) is advantageously carried out between the two precipitation stages.
• said heating step is carried out for a period of between 7 and 45 minutes and preferably between 7 and 35 minutes.
• Said heating step is advantageously carried out according to all the heating methods known to those skilled in the art.
• said preparation method comprises a second step of precipitating the suspension obtained at the end of the heating step, said second step operating by adding to said suspension at least one basic precursor chosen from sodium aluminate, potassium aluminate, ammonia, sodium hydroxide and potassium hydroxide and at least one acidic precursor selected from aluminum sulphate, aluminum chloride, aluminum nitrate, sulfuric acid, hydrochloric acid, and nitric acid, wherein at least one of the basic precursors or acid comprises aluminum, the relative flow rate of the acidic and basic precursors is selected from in order to obtain a pH of the reaction medium of between 8.5 and 10.5 and the flow rate of the aluminum-containing acidic and basic precursor (s) is adjusted so as to obtain a progress rate of the second stage of between 0.degree.
• at least one basic precursor chosen from sodium aluminate, potassium aluminate, ammonia, sodium hydroxide and potassium hydroxide and at least one acidic precursor selected from aluminum sulphate, aluminum chloride, aluminum nitrate, sulfuric
• Basic precursors comprising aluminum are sodium aluminate and potassium aluminate.
• the preferred basic precursor is sodium aluminate.
• Acidic precursors comprising aluminum are aluminum sulphate, aluminum chloride and aluminum nitrate.
• the preferred acidic precursor is aluminum sulphate.
• said second precipitation step operates with stirring.
• said second step is carried out in the absence of organic additive.
• the acidic and basic precursors are mixed, preferably in solution, in the aqueous reaction medium, in such proportions that the pH of the resulting suspension is between 8.5 and 10. 5.
• step a) of precipitation it is the relative flow rate of the acidic and basic precursors that they contain aluminum or not, which is chosen so as to obtain a pH of the reaction medium of between 8, 5 and 10.5.
• the mass ratio of said basic precursor to said acidic precursor is advantageously between 1.6 and 2.05.
• the acidic and basic precursors are also mixed in amounts to obtain a suspension containing the desired amount of alumina, depending on the final concentration of alumina to be achieved.
• said second precipitation step makes it possible to obtain 0 to 60% by weight of alumina with respect to the total amount of alumina formed at the end of the precipitation stage or steps.
• step a) of precipitation it is the flow rate of the acidic and basic precursor (s) containing aluminum which is adjusted so as to obtain a progress rate of the second stage of between 0 and 60.degree. %, the feed rate being defined as the proportion of alumina formed in said second precipitation step relative to the total amount of alumina formed from the precipitation step or steps.
• the rate of progress of said precipitation step a) is between 10 and 55% and preferably between 15 and 55%, the degree of progress being defined as the proportion of alumina formed during said second precipitation step relative to the total amount of alumina formed at the end of the two precipitation steps of the preparation process according to the invention.
• the flow rate of aluminum sulfate should be 10.5 ml / min and the sodium aluminate flow rate is 13.2 ml / min.
• the weight ratio of sodium aluminate to aluminum sulfate is therefore 1.91.
• the aluminum sulfate flow rate should be 2.9 ml / min and the sodium aluminate flow rate is 3.5 ml / min.
• the weight ratio of sodium aluminate to aluminum sulfate is therefore 1.84.
• said second heating step is carried out for a period of between 7 and 45 minutes.
• Said second heating step is advantageously carried out according to all the heating methods known to those skilled in the art.
• Said second heating step makes it possible to increase the temperature of the reaction medium before subjecting the suspension obtained in hydrothermal treatment step b).
• Said drying step is advantageously carried out at a temperature of between 20 and 50% and for a duration of between 1 day and 3 weeks or by atomization.
• the catalyst support thus obtained after the forming and calcining steps e) and f) comprises and preferably consists of at least said zeolite and at least one binder comprising at least said amorphous mesoporous alumina.
• the catalyst used in the hydrocracking process according to the invention is then advantageously obtained by adding the elements constituting the active phase.
• the elements of groups VIB, and / or the non-noble elements of group VIII, optionally the doping elements chosen from phosphorus, boron, silicon and optionally the elements of groups VB, and VII A may optionally be introduced, all or part of at any stage of the preparation, during the synthesis of the matrix, preferably during the shaping of the support, or very preferably after the shaping of the support by any method known to those skilled in the art . They can be introduced after forming the support and after or before the drying and calcining of the support.
• the deposition of boron and silicon can also be carried out simultaneously using, for example, a solution containing a boron salt and a silicon-type silicon compound.
• Group VB element sources that can be used are well known to those skilled in the art.
• niobium sources oxides, such as diniobium pentoxide Nb 2 O 5 , niobic acid Nb 2 O 5 .H 2 O, niobium hydroxides and polyoxoniobates
• niobium alkoxides can be used. of formula Nb (OR1) 3 where R1 is an alkyl radical, niobium oxalate NbO (HC 2 O 4 ) 5 , ammonium niobate.
• Niobium oxalate or ammonium niobate is preferably used.
• the final alumina concentration is 30g / L.
• the extrudates obtained are dried at 100 ⁇ during e overnight and then calcined for 2 h at 600 ⁇ C.
• the synthesis of two supports S2 and S3 is carried out according to a preparation method according to the invention in a 7L reactor and a final 5L suspension in 3 steps, two precipitation stages followed by a ripening stage. .
• the final alumina concentration is 45g / L.
• the amount of water added to the reactor is 3267 ml.
• the agitation is 350 rpm throughout the synthesis.
• the temperature of the reaction medium is maintained at 30 °.
• a second step of co-precipitation of the suspension obtained is then carried out by adding aluminum sulphate Al 2 (S0 4) at a concentration of 102g / L of Al 2 0 3 and NaAIOO sodium aluminate at a concentration of 155g / L in Al 2 O 3 .
• a solution of aluminum sulphate Al 2 (SO 4 ) is therefore added continuously to the heated suspension obtained at the end of the first precipitation step for 30 minutes at a flow rate of 7.2 ml / min.
• sodium aluminate NaAlOO in a mass ratio base / acid 1.86 so as to adjust the pH to a value of 9.
• the temperature of the reaction medium in the second step is maintained at 68 ⁇ .
• a suspension containing a precipitate of alumina is obtained.
• the suspension obtained is then subjected to a rise in temperature of 68 to 90%.
• the suspension obtained is then filtered by displacement of water on a sintered Buchner type tool and the alumina gel obtained is washed 3 times with 5 L of distilled water. Filtration time and washes is 3h.
• Table 4 characteristics of the alumina gel obtained according to Example 2.
• a gel having a dispersibility index of 100% is thus obtained.
• the alumina gel obtained is then spray dried with a 250 ⁇ inlet temperature and outlet "I SO i.
• the freeze-dried Atomi sation is called Gel # 1.
• the alumina gel obtained according to EXAMPLE 3 is dried in a ventilated study at 35 ° C. for 4 days The oven dried gel is referred to as gel n ⁇ 2.
• the paste obtained is then extruded through a 2 mm trilobal die.
• the extrudates obtained are dried at 100 ° C. overnight and then alkaline for 2 hours at 600 ° C.
• Two supports S2 and S3 each comprising 20% by weight of the zeolite USY-1 and 80% of alumina gel No. 1 and 2 are obtained.
• the characteristics of the supports S2 and S3 formed are reported in Table 5: Table 5: characteristics of the supports S2 and S3 obtained according to Example 2.
• a solution composed of molybdenum oxide, nickel hydroxycarbonate and phosphoric acid is added to the supports S1 to S3 by dry impregnation to obtain a formulation of 2.5 / 15.0 / 2 expressed in% weight of oxides relative to the amount of dry matter for the final catalysts C1 to C3.
• the extrudates are allowed to mature in an atmosphere saturated with water for 12 h, then they are dried overnight at 1 1 OC and finally calcined at 450 ⁇ for 2 hours to lead to C1 non-compliant catalysts and C2 and C3, according to the invention.
• Example 4 Comparison of catalysts C1 to C3 in hydrocracking of a vacuum distillate
• the hydrocracking test unit which comprises a fixed-bed reactor with up-flow of the feed ("up-flow") into which 50 ml of catalyst is introduced.
• the catalysts are sulphurized with an additonal straight run gas oil mixture of 4% by weight of dimethyl disulphide and 1.6% by weight of 350% aniline. It should be noted that any in situ or ex situ sulphurization method is suitable. Once the sulphurization is complete, the charge described in Table 10 can be transformed.
• the catalytic performances are expressed in relative relation to those obtained for the non-compliant reference catalyst C1 by the temperature difference which makes it possible to reach a gross conversion level of 70% (denoted T70) and by the differences in yields in gasoline and middle distillates (jet fuel and diesel) at this same gross conversion. These catalytic performances are measured on the catalyst after a period of stabilization, generally at least 48 hours, has been observed.
• the yield of jet fuel (kerosene, 150-250, below Yt Kero) is equal to the weight% of compounds having a boiling point of between 150 and 250 ° in the effluents.
• the yield of gas oil (250-380) is equal to the weight% of compounds having a boiling point of between 250 and 380 ° in ef fluents.
• the reaction temperature is set so as to reach a gross conversion CB equal to 70% by weight.
• Table 7 we have reported the reaction temperature and the yields of light and medium distillates for the catalysts described in the examples above.
• the catalysts C2 and C3, in accordance with the invention have higher catalytic performance than the non-compliant catalyst C1.
• the catalysts C2 and C3 show a gain in yield of middle distillates of respectively 1.5 and 1.6 points.
• there is no significant difference in catalytic performance between the C2 and C3 catalysts which shows that the type of drying of the alumina gel according to the invention has no impact on the catalytic performances obtained. .

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• 2015
  • 2015-12-08 FR FR1561975A patent/FR3044677B1/fr not_active Expired - Fee Related
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