WO2019098876A1 - Catalyseur d'hydrocraquage de matière première hydrocarbure - Google Patents

Catalyseur d'hydrocraquage de matière première hydrocarbure Download PDF

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WO2019098876A1
WO2019098876A1 PCT/RU2018/000378 RU2018000378W WO2019098876A1 WO 2019098876 A1 WO2019098876 A1 WO 2019098876A1 RU 2018000378 W RU2018000378 W RU 2018000378W WO 2019098876 A1 WO2019098876 A1 WO 2019098876A1
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catalyst
amorphous aluminosilicate
hydrocracking
molybdenum
tungsten
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PCT/RU2018/000378
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English (en)
Russian (ru)
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Павел Петрович ДИК
Василий Юрьевич ПЕРЕЙМА
Галина Ивановна КОРЯКИНА
Ксения Александровна НАДЕИНА
Максим Олегович КАЗАКОВ
Олег Владимирович Климов
Александр Степанович НОСКОВ
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Акционерное Общество "Газпромнефть-Омский Нпз" (Ао "Газпромнефть-Онпз")
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Publication of WO2019098876A1 publication Critical patent/WO2019098876A1/fr

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    • 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
    • B01J21/12—Silica and 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
    • 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
    • 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
    • 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
    • B01J23/888—Tungsten
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/16—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes
    • B01J31/22—Organic complexes
    • 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
    • B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
    • B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
    • B01J31/34—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of chromium, molybdenum or tungsten
    • 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
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof

Definitions

  • the invention relates to catalysts for the hydrocracking of hydrocarbons, intended for the production of kerosene and diesel fractions with low sulfur content.
  • catalysts containing nickel and molybdenum or tungsten oxides are used, supported on a carrier containing amorphous aluminosilicate, high silica zeolite Y and alumina.
  • So known catalyst [RF No 2540071], most preferably containing 10-20 May. % of tungsten or molybdenum, 1-6 May. % nickel, and its carrier contains a total of 10-50 May. % of zeolites Y and beta, and the rest is amorphous aluminosilicate, and the content of zeolite beta is 0.5-10 May.
  • the process of hydrocracking is carried out at a temperature of 300-450 ° C, a pressure of 8-20 MPa, with a ratio of hydrogen / feedstock of 200-3000 nl / kg and a bulk flow rate of feed of 0.2-5 kg * l 1 * h 1 .
  • the main disadvantage of such a catalyst and method of carrying out the hydrocracking process is the low yield of the kerosene and diesel fractions, as well as the high sulfur content in the resulting products.
  • Known catalyst most preferably containing 21 May. % W0 3 , 5 May. % NiO, and its carrier most preferably contains a total of 20-80 May. % Ultrastable zeolite Y and zeolite nizkokremnezemnogo Y or zeolite beta or zeolite ZSM-5, and the remainder a binder in the form of amorphous silica and aluminum oxide, wherein the content nizkokremnezemnogo zeolite Y, zeolite beta, zeolite ZSM-5 is 0.5-10%.
  • the process of hydrocracking is carried out at a temperature of 300-450 ° C, a pressure of 8-20 MPa, with a ratio of hydrogen / raw materials of 250-2000 nl / kg and a bulk flow rate of raw materials of 0.5-5 kg * l 1 * h 1 .
  • the main disadvantage of such a catalyst and method of carrying out the hydrocracking process is the low yield of the kerosene and diesel fractions, as well as the high sulfur content in the resulting products.
  • catalysts containing a three-component system Ni + Mo + W
  • So known catalyst [RF N ° 2 245 737], containing, May. %: hydrogenating components 15-30% (oxides of nickel, molybdenum and tungsten with a mass ratio of 25:35:40), acid component (aluminum fluoride) 20-40 promoter (boron and / or zirconium oxide) 1-4, binder (oxide aluminum, aluminosilicate, clay or their mixture) up to 100%.
  • the process of hydrocracking is carried out at a temperature of 380-430 ° C, a pressure of 3-10 MPa, with a ratio of hydrogen / feedstock of 250-1000 nm 3 / m 3 and a space velocity of feed of raw materials 1-3 h 1 .
  • the main disadvantage of such a catalyst and method of carrying out the hydrocracking process is the low yield of the kerosene and diesel fractions, as well as the high sulfur content in the resulting products.
  • catalysts containing C 3 -C 12 polyhydroxy compounds as modifying additives can be used.
  • the hydrocracking catalyst for hydrocarbon feedstock [WO 2013092806 Al, B01J21 / 12, C10G47 / 12, 27/06/2013], which includes nickel, molybdenum or tungsten, a carrier based on amorphous aluminosilicate and C 3 -C 12 polyhydroxy compound .
  • the components in the catalyst are most preferably contained in the following concentrations, May. %: Nickel 3-6, molybdenum 10-16 or tungsten 15-22, sucrose and / or gluconic acid 5-20.
  • the catalyst after the application of the active metals is dried at a temperature of not more than 200 ° C.
  • the hydrocracking process is carried out at a temperature of 300-450 ° C, a pressure of 8-20 MPa, with a hydrogen / feedstock ratio of 200-3000 nl / kg and a space feed rate of 0.2-5 kg * l 1 * h '1 .
  • the main disadvantage of such a catalyst is the low yield of kerosene and diesel fractions, as well as the high sulfur content in the resulting products.
  • the closest in technical essence to the claimed catalyst is a catalyst for the hydrocracking of hydrocarbons [RF JVo 2607905], which includes nickel, molybdenum, aluminum and silicon.
  • the components in the catalyst are contained in the following concentrations, May. %: [Ni (H 2 0) x (L) y ] 2 [Mo 4 O ll (C 6 H 5 0 7 ) 2 ] 13.1-23.3, amorphous aluminosilicate - 40.0-61.3; g-A1 2 0 3 - the rest, which corresponds to the content in the calcined at 550 ° C catalyst, May. %: MoO 3 - 7.0-13.0, O - 1.8-3, 4, amorphous aluminosilicate - 43.1-66.9; g-A1 2 0 3 - the rest.
  • the main disadvantage of the prototype, as well as other known catalysts, is the low yield of kerosene and diesel fractions, as well as the high sulfur content in the resulting products.
  • the invention solves the problem of creating an effective catalyst for the hydrocracking of hydrocarbons.
  • the technical result is a high hydrodesulfurization activity and the textural and acidic characteristics of the catalyst that are optimal for the hydrocracking of hydrocarbon feedstock, providing kerosene and diesel fractions with high yield and low sulfur content.
  • a catalyst that contains nickel, molybdenum, tungsten, aluminum and silicon.
  • the molar ratio of W / (Mo + W) in the catalyst should be in the range of 0.3-0.7.
  • the catalyst has a pore volume of 0.61-0.80 cm 3 / g, a specific surface area of 224-263 m / g and an average pore diameter of 10.3-11.8 nm and is a particle with a cross-section in the form of a trefoil, quatrefoil or a circle with a diameter of 1.2 circumference -2, 5 mm and a length of up to 20 mm, having a volumetric mechanical strength, determined by the method of Shell SMS 1471, not less than 1, 0 MPa.
  • aluminosilicates with a Si / Al mass ratio of 0.6 to 0.85 can be used, characterized by X-ray diffraction patterns containing a broad peak in the 16.5-33.5 ° range with a maximum of 23.1-23.4 °.
  • a distinctive feature of the proposed catalyst in comparison with the prototype is that the catalyst contains, [Ni (H 2 0) x (L) y ] 2 [Mo 4 0 ll (C 6 H 5 0 7 ) 2 ] 6.2-14.9, Ni ( NH 4 ) a [H b W 2 0 5 (C 6 H 5 0 7 ) 2 ] 10.2-
  • the molar ratio of W / (Mo + W) in the catalyst should be in the range of 0.3-0.7.
  • the yield of the content and the mass ratio of the catalyst components beyond the claimed limits leads to a decrease in the activity of the catalyst in the target hydrocracking reactions, to a decrease in the selectivity of the catalyst with respect to the kerosene and diesel fractions and to a decrease in the activity of the catalyst in hydrodesulfurization.
  • the claimed chemical composition of the catalyst causes a high activity in the target hydrocracking reactions and a high selectivity for relative to the kerosene and diesel fractions.
  • the presence of bimetallic compounds [Ni (H 2 0) x (L) y ] 2 [Mo 4 O ll (C 6 H 5 0 7 ) 2 ] and Ni (NH 4 ) a [H b W 2 05 (C 6 H50 7 ) 2] in the claimed concentrations provides further formation in the catalyst, during its operation in hydrocracking, highly active particles of the sulfide component — NiMoS and NiWS phases of type II in the form of particles that are optimal for catalysis of morphology localized in the pores accessible to all molecules to be converted .
  • nickel-molybdenum and nickel-tungsten with a molar ratio of W / (Mo + W) from 0.3 to 0.7 leads to easier sulfiding of tungsten-containing compounds by adding building tungsten sulfide around molybdenum sulfide to form particles of the core-shell type - a trimetallic NiMoWS phase of type II, possessing maximum activity in the hydrogenation of aromatic compounds.
  • each essential feature is necessary, and their combination is sufficient to achieve a new quality, non-characteristic in disunity, that is, the task is achieved not by the sum of the effects, but by the new supereffect of the sum of the signs.
  • the amount of aluminum hydroxide and aluminosilicate powder is taken taking into account that the mass content of amorphous aluminosilicate in the carrier was 50-70 May. %
  • the amount of water added to make a paste depends on the moisture content of the initial powders and is approximately 0.8-1.3 ml / g.
  • the amount of nitric acid is calculated depending on the amount of g-A1 2 0 3 so that the acid modulus is from 0.05 to 0.7, more preferably from 0.1 to 0.5.
  • the resulting paste is extruded through a die with holes, the shape and dimensions of which provide the production of granules with a cross-section in the form of a trefoil, quatrefoil or a circle with a circumference of 1.2-2.5 mm.
  • the obtained wet carrier is dried at a temperature of 100-150 ° C and calcined at a temperature of 500-600 ° C.
  • the result is a homogeneous carrier of white color, which is a granule with a cross with section in the form of a trefoil, a four-leaf or a circle with a circumference of 1.2-2.5 mm and a length of 2-20 mm.
  • the resulting solution is impregnated with a carrier containing amorphous aluminosilicate, using either the impregnation of the carrier according to moisture capacity, or from an excess of solution, or vacuum impregnation. Impregnation is carried out at a temperature of 15-90 ° C for 5-60 minutes with occasional stirring, in the case of impregnation from an excess solution, or vacuum impregnation, after impregnation an excess solution is drained from the catalyst and used to prepare the following catalyst batches. After impregnation, the catalyst is dried in air at a temperature of 100-250 ° C. The result is a catalyst, the characteristics of which fully correspond to the claimed intervals.
  • the catalyst is tested in the hydrocracking of vacuum gas oil with a sulfur and nitrogen content of 2.81 May. % and 0.093 May. %, respectively, the distillation temperature of 5% vol. 292 ° C and a distillation temperature of 95% vol. 527 ° C.
  • the catalyst is sulfided by heating it in a stream of hydrogen and a sulfiding mixture, which is a straight-run diesel fuel with a sulfur content of 1.45% S, to which dimethyl disulfide with a concentration of 12 g / l is additionally added.
  • the resulting catalyst contains, may. %:
  • a portion of the catalyst with a volume of 30 cm is mixed with 120 cm of silicon carbide (0.1-0.3 mm), placed in a stainless steel flow reactor and heated in a stream of hydrogen and a sulfiding mixture, which is a straight-run diesel fuel with a sulfur content of 1.45 % S, which additionally added dimethyl disulfide with a concentration of 12 g / l.
  • Sulfidation is carried out at 3.5 MPa, the flow rate of the sulfiding mixture is 2 hours and the volume ratio of hydrogen / sulfiding mixture is 500 nm / m 4 h at 240 ° C, and then 4 h at 260 ° C and then 8 h at 340 ° C.
  • the hydrocracking process is carried out at a temperature of 390 ° C, a pressure of 12 MPa, a volumetric flow rate of the raw material of 0.6 h 1 , a volume ratio of hydrogen / raw material of 1100 m 3 (at U.) / m 3 .
  • a carrier is prepared containing 50% by weight of amorphous aluminosilicate as in Example 1.
  • An aqueous solution is prepared containing 13.9 g of [Ni (H 2 0) x (L) y ] 2 [Mo 4 0 (C 6 H 5 0 7 ) 2 ] and 9.5 g Ni (NH 4 ) a [H b W 2 0 5 (C 6 H 5 0 7 ) 2 ], for which purpose 9.62 g of citric acid monohydrate C 6 H 8 0 are successively dissolved in 40 ml of water at 70 ° C and stirring.
  • the IR spectrum of the resulting solution contains peaks characteristic of Ni (NH 4 ) a [H b W 2 0 5 (C 6 H 5 0 7 ) 2 ] and [Ni (H 2 0) x (L) y ] 2 [Mo 4 O ll (C 6 H 5 0 7 ) 2 ] (table 1).
  • the catalyst is dried in air at 120 ° C.
  • the radiograph of the catalyst obtained contains a peak with a maximum of 23.1 °, corresponding to amorphous aluminosilicate with a Si / Al mass ratio of 0.85.
  • the resulting catalyst contains, may. %:
  • the catalyst has a pore volume of 0.69 cm 3 / g, a specific surface area of 247 m 2 / g and an average pore diameter of 1 1.0 nm and is a particle with a cross-section in the shape of a trefoil with a diameter of a circumcircle of 1.0-1.6 mm and a length of up to 20 mm .
  • the volumetric mechanical strength of the catalyst measured by the method of Shell SMS 1471, is 1.15 MPa.
  • the IR spectrum of the resulting solution contains peaks characteristic of Ni (NH 4 ) a [H b W 2 0 5 (C 6 H 5 0 7 ) 2 ] and [Ni (H 2 0) x (L) y ] 2 [Mo 4 On (C 6 H 5 0 7 ) 2 ] (table 1).
  • the catalyst is dried in air at 120 ° C.
  • the resulting catalyst contains, may. %:
  • the catalyst has a pore volume of 0.66 cm 3 / g, a specific surface area of 240 m 2 / g and an average pore diameter of 10.3 nm and is a particle with a cross-section in the shape of a trefoil with a diameter of a circumscribed circle of 1.0-1.6 mm and a length of up to 20 mm.
  • the volumetric mechanical strength of the catalyst measured by the method of Shell SMS 1471, is 1.15 MPa.
  • the IR spectrum of the resulting solution contains peaks characteristic of Ni (NH 4 ) a [H b W 2 0 5 (C 6 H 5 0 7 ) 2 ] and [Ni (H 2 0) x (L) y ] 2 [Mo 4 0 11 (C 6 H 5 0 7 ) 2 ] (table 1).
  • 70 g of the carrier is impregnated on the capacity of 72 ml of the resulting solution.
  • the catalyst is dried in air at 120 ° C.
  • the resulting catalyst contains, may. %:
  • the catalyst has a pore volume of 0.64 cm 3 / g, a specific surface area of 236 m 2 / g and an average pore diameter of 10.7 nm and is a particle with a cross-section in the shape of a trefoil with a diameter of a circumscribed circle of 1.0-1.6 mm and length up to 20 mm.
  • the volumetric mechanical strength of the catalyst measured by the method of Shell SMS 1471, is equal to 1.10 MPa.
  • An aqueous solution is prepared containing 13.4 g [Ni (H 2 0) x (L) y ] 2 [Mo 4 On (C 6 H 5 0 7 ) 2 ] and 21.5 r Ni (NH 4 ) a [H b W 2 0 5 (C 6 H 5 0 7 ) 2 ], for which purpose 14.99 g of citric acid monohydrate C 6 H 8 0 7 hH 2 0, 5.86 g of basic nickel carbonate NiC0 3 mNi are successively dissolved in 40 ml of water at 70 ° C and stirring 0H) 2 nH 2 0, 12.58 g of ammonium paratungstate (NH 4 ) 6 W 7 0 24 x4H 2 0r and 8.41 g of ammonium paramolybdate (NH 4 ) 6 Mo 7 0 24 c 4H 2 0.
  • the resulting catalyst contains, may. %:
  • the catalyst has a pore volume of 0.61 cm 3 / g, a specific surface area of 224 m 2 / g and an average pore diameter of 1 1.8 nm and is a particle with a section in the form of a circle with a diameter of a circumscribed circle of 1.0-1.6 mm and a length of up to 20 mm .
  • the volumetric mechanical strength of the catalyst measured by the method of Shell SMS 1471, is equal to 1.28 MPa.
  • the powder of amorphous aluminosilicate with a mass ratio of Si / Al 0.6, having a broad peak in the region of 16.5-33.5 ° with a maximum of 23.4 °, is calcined at a temperature of 700 ° C for 4 hours.
  • the resulting catalyst contains, may. %:
  • the catalyst has a pore volume of 0.80 cm 3 / g, a specific surface area of 263 m 2 / g and an average pore diameter of 1 1.4 nm and is a quadruple-shaped particle with a circumferential diameter of 1.0-1.6 mm and a length of up to 20 mm .
  • the volumetric mechanical strength of the catalyst measured by the method of Shell SMS 1471, is 1.05 MPa.
  • compositions of the complex compounds Ni (NH 4 ) a [H b W 2 0 5 (C 6 H 5 0 7 ) 2 ] and [M (H 2 0) x (b) y ] 2 [Mo 4 0n (C 6 H 5 0 7 ) 2 ] in examples 1-6 are given in table 3.
  • the proposed catalyst due to its chemical composition has high activity and selectivity to the fraction with an initial boiling point of 130 ° C and a final boiling point of 360 ° C, i.e. to the kerosene and diesel fractions, providing a significantly higher yield of kerosene and diesel fractions than when using the prototype catalyst in the hydrocracking of hydrocarbons.
  • the sulfur content in the resulting fraction of 360 ° ⁇ -boiling point is significantly lower than when using the prototype catalyst. Table 1.

Abstract

L'invention concerne des catalyseurs d'hydrocraquage de matières premières hydrocarbures pour obtenir des fractions de gasoil et de kérosène à faible teneur en sulfures. L'invention porte sur une solution au problème de création d'un catalyseur efficace d'hydrocraquage de matière première hydrocarbure. L'invention concerne un catalyseur qui comprend simultanément du molybdène et du tungstène sous forme de composés bimétalliques [Ni(H2O)х(L)y]2[Mo4O11(C6H5O7)2] и Ni(NH4)a[HbW2O5(C6H5O7)2], dans laquelle: L et С6Н5О7 sont une forme partiellement exempte de protons d'acide citrique; х=0 ou 2; y=0 ou 1; а=0, 1 ou 2; b=2-а; du silicium sous forme de silicate d'aluminium amorphe, de l'aluminium sous forme de γ-Al2O3 et de silicate d'aluminium amorphe, les composants dans le catalyseur étant contenus dans les proportions suivantes, en % en masse : [Ni(H2O)x(L)y]2[Mo4O11(C6H5O7)2] - 6.2-14.9, Ni(NH4)a[HbW2O5(C6H5O7)2] - 10.2-23.3, silicate d'aluminium amorphe 33.4-50.9; γ-Al2O3 pour le reste, ce qui correspond à la teneur dans un catalyseur recuit à 550°С, en % en masse: MoO3 3.6-8.4, WO3 5.8-13.5, NiO 3.1-3.9, silicate d'aluminium amorphe 38.3-56.9, γ-Al2O3 constituant le reste. Le tungstène et le molybdène faisant partie de la composition du catalyseur sont contenus dans un rapport molaire W/(Mo+W) de 0,3 à 0,7.
PCT/RU2018/000378 2017-11-16 2018-06-07 Catalyseur d'hydrocraquage de matière première hydrocarbure WO2019098876A1 (fr)

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RU2017140003A RU2662239C1 (ru) 2017-11-16 2017-11-16 Катализатор гидрокрекинга углеводородного сырья
RU2017140003 2017-11-16

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Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2013092806A1 (fr) * 2011-12-23 2013-06-27 Shell Internationale Research Maatschappij B.V. Procédé pour la préparation de catalyseur d'hydrocraquage
RU2607905C1 (ru) * 2015-11-05 2017-01-11 Федеральное государственное бюджетное учреждение науки Институт катализа им. Г.К. Борескова Сибирского отделения Российской академии наук Катализатор гидрокрекинга углеводородного сырья
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