WO2020130881A1 - Catalyseur d'hydropurification de carburant diesel - Google Patents

Catalyseur d'hydropurification de carburant diesel Download PDF

Info

Publication number
WO2020130881A1
WO2020130881A1 PCT/RU2019/000973 RU2019000973W WO2020130881A1 WO 2020130881 A1 WO2020130881 A1 WO 2020130881A1 RU 2019000973 W RU2019000973 W RU 2019000973W WO 2020130881 A1 WO2020130881 A1 WO 2020130881A1
Authority
WO
WIPO (PCT)
Prior art keywords
catalyst
carrier
rest
solution
norbergite
Prior art date
Application number
PCT/RU2019/000973
Other languages
English (en)
Russian (ru)
Inventor
Олег Владимирович Климов
Елена Александровна СТОЛЯРОВА
Владимир Владимирович ДАНИЛЕВИЧ
Олеся Олеговна ЗАИКИНА
Вадим Анатольевич ЯКОВЛЕВ
Александр Степанович НОСКОВ
Original Assignee
Акционерное Общество "Газпромнефть-Омский Нпз" (Ао "Газпромнефть-Онпз")
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Акционерное Общество "Газпромнефть-Омский Нпз" (Ао "Газпромнефть-Онпз") filed Critical Акционерное Общество "Газпромнефть-Омский Нпз" (Ао "Газпромнефть-Онпз")
Publication of WO2020130881A1 publication Critical patent/WO2020130881A1/fr

Links

Classifications

    • 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
    • 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
    • B01J23/882—Molybdenum and cobalt
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/16—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr
    • B01J27/18—Phosphorus; Compounds thereof containing oxygen, i.e. acids, anhydrides and their derivates with N, S, B or halogens without carriers or on carriers based on C, Si, Al or Zr; also salts of Si, Al and Zr with metals other than Al or Zr
    • 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
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with chromium, molybdenum, tungsten or polonium
    • B01J27/19—Molybdenum
    • 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
    • B01J31/18—Catalysts comprising hydrides, coordination complexes or organic compounds containing coordination complexes containing nitrogen, phosphorus, arsenic or antimony as complexing atoms, e.g. in pyridine ligands, or in resonance therewith, e.g. in isocyanide ligands C=N-R or as complexed central atoms
    • 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
    • B01J32/00—
    • 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
    • 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 hydrotreating catalysts for the production of low sulfur oil products.
  • catalysts containing cobalt and molybdenum oxides supported on alumina are used for hydrodesulfurization of petroleum feeds.
  • So known catalyst hydrodesulfurization [RF Application N ° 2002124681, C10G45 / 08, B01J23 / 887, 09.16.2002], containing in its composition cobalt oxide, molybdenum oxide and alumina, characterized in that it has a ratio of components, May. %: cobalt oxide 3, 0-9.0, molybdenum oxide 10.0-24.0, aluminum oxide the rest, specific surface 160-250 m 2 / g, mechanical crushing strength 0.6-0.8 kg / mm 2 .
  • the hydrotreatment process is carried out at a temperature of 310-340 ° C, a pressure of 3, 0-5.0 MPa, with a hydrogen / feed ratio of 300-500 nm 3 / m 3 and a bulk feed rate of 1.0-4.0 h 1 .
  • the main disadvantage of such a hydrotreating catalyst is the high sulfur content in the resulting products.
  • the method of depositing active metals on an already formed support has been used to prepare hydrotreating catalysts.
  • alumina with a certain size and shape of granules and certain texture characteristics is most often used.
  • the carrier is often modified with various additives, including boron compounds.
  • the modifying additives are introduced into the carrier either before the stage of its formation, by coprecipitation of modifiers and aluminum from joint solutions [Journal of Catalysis 115 (1989) 441-451], or by mixing aluminum hydroxide with a modifying compound at the stage of preparing the paste for molding [US No. 6147432], or the additive is introduced by impregnation into a molded carrier, followed by drying and calcination [Catalysis Today 107-108 (2005) 551-558].
  • active metals most often Co, Ni, Mo, and W
  • introduction of active metals into the composition of the catalyst is carried out by impregnating the formed support with aqueous solutions of their salts.
  • they can be used as separate deposition of active metals by impregnation in several stages [RF N ° N ° 2242501, 2246987], and their deposition from joint solutions stabilized by various agents [RF NaNs 2073567, 2216404, 2306978].
  • a carrier with improved texture characteristics is used in their preparation, while the specific surface area of the catalyst reaches 300 m 2 / g and the average pore diameter lies in the range of 8-11 nm, which provides good access of sulfur-containing molecules to the active centers of the catalyst .
  • the known catalyst [RF N ° 2192923, C10G45 / 08, B01J27 / 188, B01J35 / 10, 11.20.2002] based on aluminum oxide, which contains, in terms of the weight content of the oxide: 2-10 wt.% cobalt oxide CoO, 10-30 wt.% molybdenum oxide MoO3 and 4-10 wt.% phosphorus oxide P2O5, with a surface area according to the BET method in the range of 100-300 m 2 / g and an average pore diameter in the range of 8-11 nm.
  • a known catalyst for hydrotreating oil fractions [RF N ° 2286846, B01J23 / 78, B01J23 / 83, C10G45 / 08, 11/10/2006], which contains oxides of cobalt, molybdenum, sodium, lanthanum, boron and phosphorus and has the following composition, wt.% : CoO 2, 5-4.0; MoOs 8.0-12.0; AgO 0.01-0.08; Lagos 1, 5-4.0; P2O5 2, 0-5.0; B2O3 0.5-3.0; AO3 - the rest.
  • a known catalyst for hydrodesulfurization of a diesel fraction [RF N ° 2313392, B01J37 / 02, B01J21 / 02, C10G45 / 08, 10/13/2006], having a pore volume of 0.3-0.7 ml / g, a specific surface area of 200-350 m 2 / g and an average pore diameter of 9-13 nm, containing the following components, May.
  • % cobalt compounds with a concentration of 2, 5-7, 5 in terms of CoO, molybdenum compounds with a concentration of 12-25 in terms of MoOz, citric acid with a concentration of 15-35, boron compounds 0, 5-3.0 in terms of B2O3, aluminum oxide AI2O3 - the rest, while cobalt, molybdenum, citric acid and boron can be part of complex compounds of various stoichiometry.
  • a known hydrotreating catalyst [US Pat. RF N ° 2472585, B01J23 / 882, 01/20/2013], containing, wt.%: Mo - 8.0-15.0; Co or Ni - 2.0-0.5.0; S - 5.0-15.0; B - 0.5-2.0; C - 0.5-7.0; ABO3 - the rest, while the carrier contains, wt.%: B-0, 7-3.0; ABO3 - the rest and has a specific surface area of 170-300 m 2 / g, a pore volume of 0.5-0.95 cm 3 / g and an average pore diameter of 7-22 nm, and is a particle with a cross section in the form of a trefoil with a diameter of the circumscribed circle 1.0 - 1.6 mm and a length of up to 20 mm, having a mechanical strength of 2.0-0-2.5 kg / mm.
  • catalyst containing, wt.%: [Co (H20) 2 (SBH507)] 2 [Mo40c (SBH5 ( > 7) 2 ] 33.0-43.0%; carrier - the rest; while the carrier contains, wt.%: borate aluminum ABBO with the structure of norbergite - 5.0-25.0; sodium - not more than 0.03; g-ABO3 - the rest.
  • the catalyst has a specific surface area of 130-180 m 2 / g, pore volume 0.35-0.65 cm 3 / g, the average pore diameter of 7-12 nm, and represents particles with a cross section in the form of a circle, shamrock or four-leaf with a diameter of the circumscribed circle of 1.0 - 1.6 mm and a length of up to 20 mm After sulfidation by known
  • the main disadvantage of the known catalyst is that it has a non-optimal chemical composition, which leads to its low activity in the hydrotreatment of diesel fuel.
  • the present invention solves the problem of creating an improved hydrotreating catalyst, characterized by the optimal chemical composition.
  • EFFECT obtaining a catalyst having activity in target reactions occurring during hydrotreating of mixed diesel fuel containing distillates of secondary oil refining processes.
  • hydrocarbon hydrotreating catalyst which contains, wt.%: [Co (H20) 2 (SbN507)] 2 [Mo40ts (SbN5S> 7) 2] - 7.7-
  • the carrier is the rest; however, the medium contains May. %: aluminum borate ABBO b with the structure of norbergite - 5.0-25.0; g-AO3 - the rest.
  • the catalyst has a specific surface area of 120-190 m 2 / g, a pore volume of 0.35-0.65 cm 3 / g, an average pore diameter of 7-12 nm, and is a particle with a cross-section in the form of a circle, trefoil or four-leaf with the diameter described circles 1, 0-1.6 mm and a length of up to 20 mm.
  • the catalyst contains, wt.%: Mo - 10.0-16.0; Co - 2, 7-4, 5; P-0.8-1, 8; S 6.7-10.8; the carrier is the rest.
  • a distinctive feature of the proposed catalyst in comparison with the prototype is its chemical composition, namely, that the inventive catalyst contains, May.
  • the second distinguishing feature of the proposed catalyst in comparison with the prototype is that it has a specific surface area of 120-190 m 2 / g, a pore volume of 0.35-0.65 cm 3 / g, an average pore diameter of 7-12 nm, and represents particles with a cross section in the form of a circle, trefoil or four-leaf with a diameter of the circumscribed circle 1, 0-1.6 mm and a length of up to 20 mm.
  • the inventive chemical composition of the catalyst determines the activity in the target reactions occurring during hydrotreatment of hydrocarbons.
  • the presence in the catalyst composition of phosphorus and boron compounds in the form of cobalt salt diphosphate pentamolybdate Co 2 [H 2 P 2 Mo50 2 s] and aluminum borate A1zBO b with a norbergite structure with the claimed concentration provides an acidity level that promotes the efficient conversion of nitrogen compounds that inhibit the conversion of sulfur-containing compounds .
  • PTAG hydrargillite
  • IC SB RAS centrifugal thermal activation technology
  • TU 2175-040-03533913-2007 any other technology providing PTAG with the following characteristics: mass fraction of the X-ray amorphous phase,%, not less than 80; the proportion of weight loss during calcination at (900 ⁇ 20) ° C,% - 10-12; specific surface, m 2 / g, not less than 120; total pore volume (moisture capacity), cm 3 / g, not less than 0.1; mass fraction of gibbsite (hydrargillite),%, not more than 5; mass fraction of sodium oxide,%, not more than 0.5.
  • a portion is crushed in a planetary mill to particles with an average size of 20 microns.
  • a portion of the ground powder is hydrated with stirring for two hours in weakly concentrated nitric acid solutions heated to 50 ° C (acid module 0.03). Then the resulting suspension is filtered under vacuum and washed repeatedly with distilled water. The result is a wet cake.
  • Hydrothermal treatment of the washed precipitate is carried out in an autoclave in aqueous solutions of nitric acid with the addition of a given amount of boric acid at a solution temperature above 100 ° C. After completion of the hydrothermal treatment, the solution is cooled to room temperature, the autoclave is unloaded, the contents of the vessel are repulped with distilled water to obtain a suspension suitable for spray drying. Next, drying is carried out on a spray dryer at an air inlet temperature of 280 ° C and continuous suspension stirring. The finished powder of boron-containing aluminum hydroxide is discharged from a glass of a cyclone dust collector of a spray dryer.
  • the ammonia solution was prepared as follows so that the amount of ammonia water 25% was 1.5 ml per 40 g of powder after spray drying.
  • the finished plastic mass is loaded from the mixer into the molding cylinder of the laboratory extruder and pressed through the hole of the die, providing extrudates of the finished carrier with a cross-section in the shape of a circle, trefoil or four-leaf with a size from the top of the trefoil to the middle of the base from 1.0 to 1.6 mm.
  • heat treatment of the extrudates is carried out, including drying and calcining.
  • Extrudates are dried in an oven at a temperature of (110 ⁇ 10) ° ⁇ for 2 hours.
  • Heat treatment is carried out in a muffle furnace with compressed air supplied to the furnace.
  • the extrudates in a porcelain cup were placed in an oven and calcined at a temperature of (550 ⁇ 10) ° ⁇ for 4 h.
  • the finished carrier contains, wt.%: Aluminum borate A1zVO b with the structure of norbergite - 5.0-25.0; g-ABO3 - the rest, and has a specific surface area of 200-280 m 2 / g, a pore volume of 0.6-0, 8 cm 3 / g, an average pore diameter of 7-12 nm, and represents particles with a cross section in the form of a circle, trefoil or quatrefoil with a diameter of the circumscribed circle of 1.0-1.6 mm and a length of up to 20 mm.
  • Part of the aluminum borate support structure AVO b norbergita represents a particle size from 10 to 200 nm, characterized by interplanar spacings 3.2 and 2.8 A, with an angle between 53.8 °.
  • a supported catalyst is prepared.
  • an impregnation solution is prepared containing two bimetallic complex compounds in the given ratios — the cobalt salt of molybdenum citrate [Co (H20) 2 (SBH507)] 2 [Mo40c (SBN507) 2] and the cobalt salt of pentamolybdate diphosphate Cog ⁇ grgMozOgz].
  • the specified amounts of ammonium paramolybdate (NH 4 ) 6Mq7q 24 ⁇ 4H 2 0, cobalt (II) of the main carbonate CoCO3 » tCO (OH) 2 * pN 2 0, orthophosphoric acid, citric acid are weighed out monohydrate.
  • a measured cylinder measures the specified amount of distilled water.
  • a measured amount of water is poured into the flask and the anchor of the magnetic stirrer is placed.
  • the flask is placed on the heating surface of a heated magnetic stirrer.
  • the rotation speed of the mixer is set at 300 rpm and the solution temperature is 60 ° C.
  • a predetermined amount of phosphoric acid is added, a measured amount of citric acid is loaded into the flask and mixed under visual inspection. Then, in a flask, a portion of ammonium paramolybdate is added to a solution of citric acid with constant stirring and maintaining the solution temperature (60 ⁇ 5) ° ⁇ .
  • the solution contains cobalt and molybdenum in the form of a bimetallic complex compound [Co (H20) 2 (SbH507)] 2 [Mo40c (SbH507) 2], as well as cobalt, molybdenum and phosphorus in the form of cobalt salt diphosphate pentamolybdate ⁇ 02 ⁇ 2 ⁇ 2 ⁇ 05 ⁇ 23] ⁇
  • the prepared solution is poured into a calibrated graduated cylinder, after which the volume of the solution is adjusted to a predetermined amount by the addition of distilled water.
  • the resulting solution is impregnated with a boron-containing carrier, while the carrier is impregnated with respect to moisture capacity.
  • the impregnation is carried out at a temperature of 15-70 ° C for 25-60 minutes with periodic stirring.
  • the catalyst is dried in air at a temperature of 100-200 ° C.
  • a catalyst is obtained containing, wt.% [Co (H20) 2 (SbH 5 07)] 2 [Mo40c (SbH 5 07) 2] - 7.7-32.0; ⁇ 02 ⁇ 2 ⁇ 2 ⁇ 05 ⁇ 23] - 11.1 - 29.0; the carrier is the rest; wherein the carrier contains, wt.%: aluminum borate ABBO with a norbergite structure - 5.0-25.0; g-AO3 - the rest.
  • the catalyst has a specific surface area of 120-190 m 2 / g, a pore volume of 0.35-0.65 cm 3 / g, an average pore diameter of 7-12 nm, and is a particle with a cross-section in the form of a circle, trefoil or four-leaf with the diameter described circumference 1.0-1.6 mm and a length of up to 20 mm.
  • the catalyst contains, wt.%: Mo - 10.0-16.0; Co - 2, 7-4, 5; P-0.8-1, 8; S 6.7-10.8; the carrier is the rest; however, the medium contains May. %: aluminum borate ABBO b with the structure of norbergite - 5.0-25.0; g-AO3 - the rest.
  • Example 1 According to a known solution [Pat. RF N ° 2626398].
  • a carrier is prepared, for which 150 g of the product of the thermal activation of hydrargillite is ground in a planetary mill to particles ranging in size from 20-50 microns.
  • the powder is hydrated with stirring and heating in a solution of nitric acid with a concentration of 0.5%.
  • the suspension on a funnel with a paper filter is washed with distilled water to a residual sodium content in the powder of not more than 0.03%.
  • the washed and pressed cake is transferred to an autoclave, to which a solution of 2.3 g of boric acid in 1 liter of a 1.5% solution of nitric acid, having a pH of 1.4, is added.
  • the autoclave is heated to 150 ° C and held for 12 hours.
  • the autoclave is cooled to room temperature and the suspension obtained is dried on a spray dryer at an air inlet temperature of 155 ° C and the suspension is continuously mixed, the dried powder is collected in the receiving tank of the dryer.
  • a sample of 150 g of powder is placed in a trough of a mixer with Z-shaped blades, peptized with a 2.5% aqueous solution of ammonia, and then extruded at a pressure of 60.0 MPa through a die, providing particles with a cross section in the form of a trefoil with a diameter of the circumference described 1.6 mm.
  • the formed granules are dried at a temperature of 120 ° C and calcined at a temperature of 550 ° C.
  • the result is a carrier, containing, may. %: aluminum borate ABBO b with the structure of norbergite - 5.0; y-abos - the rest.
  • the catalyst contains, wt.%: [Co (H20) 2 (SBN507) MMo40c (SBN507) 2] -
  • 38.4 media - the rest; wherein the carrier contains, wt.%: aluminum borate ABO b with the structure of norbergite - 5.0; g-AO3 - the rest.
  • the catalyst has a specific surface area of 150 m 2 / g, a pore volume of 0.55 cm 3 / g, an average pore diameter of 13 nm, and represents particles with a cross section in the form of a trefoil with a diameter of the circumscribed circle of 1.6 mm and a length of up to 20 mm.
  • the aluminum borate catalyst ALBO 6 with the structure of norbergite is a particle with sizes from 10 to 200 nm, characterized by interplanar distances of 3.2 and 2.8 A, with an angle between them of 53.8 °.
  • the catalyst is sulfidized according to one of the known methods.
  • the catalyst is sulfided virgin diesel fraction containing additionally 1.5 wt% sulphiding agent -.
  • DMDS Dimethyl disulfide
  • the result is a catalyst that contains, wt.%: Mo - 12.5; Co - 3.85; S is 8.3; the carrier is the rest; at this carrier contains, wt.%: aluminum borate ABBO b with the structure of norbergite - 5.0; g-AO3 - the rest.
  • the catalyst is tested in the hydrotreating of mixed diesel fuel prepared by mixing, vol.% - 87 - straight-run diesel fraction; 11 - light gas oil catalytic cracking, 2 - light gas oil delayed coking.
  • the feed contains 0.374% sulfur, 200 ppm nitrogen, has a density of 0.866 g / cm 3 , a boiling range of 186-360 ° C, T95 - 350 ° C.
  • the carrier is prepared analogously to example 1.
  • the result is a carrier containing may. %: aluminum borate ABBO b with the structure of norbergite - 5.0; g-AO3 - the rest.
  • the catalyst contains, wt.%: [Co (H20) 2 (SBN507)] 2 [Mo40c (SBN507) 2] -
  • the catalyst has a specific surface area of 180 m 2 / g, a pore volume of 0.65 cm 3 / g, an average pore diameter of 12 nm, and represents particles with a cross section in the form of a trefoil with a diameter of the circumscribed circle of 1.6 mm and a length of up to 20 mm.
  • a catalyst which contains wt.%: Mo - 10.0; Co - 2.7; P-0.8; S 6.7; the carrier is the rest; however, the medium contains May. %: aluminum borate ABBO b with the structure of norbergite - 5.0; g-AO3 - the rest.
  • the carrier is prepared according to a procedure similar to Example 2, with the difference that the washed and pressed cake is transferred to an autoclave, to which a solution of 5.98 g of boric acid in 1 liter of a 1.5% solution of nitric acid is added. Granulation is carried out through a die, providing particles with a cross section in the form of a trefoil with a diameter of the circumscribed circle of 1.3 mm. The remaining operations and loading of components during preparation of the media are similar to examples 1 and 2.
  • the catalyst contains, wt.%: [Co (H20) 2 (SbH507)] 2 [Mo40c (C b H507) 2] - 15.4; Co2 [H 2 P2Mo 5 02s] - 15.3; the carrier is the rest; wherein the carrier contains, wt.%: aluminum borate A1zVO b with the structure of norbergite - 12.0; g-AO3 - the rest.
  • the catalyst has a specific surface area of 150 m 2 / g, a pore volume of 0.55 cm 3 / g, an average pore diameter of 11 nm, and represents particles with a cross section in the form of a trefoil with a diameter of the circumscribed circle of 1, 3 mm and a length of up to 20 mm.
  • a catalyst which contains May. %: Mo - 12.0; Co - 3.2; P-1.0; S is 8.1; the carrier is the rest; however, the medium contains May. %: aluminum borate A1zVO b with the structure of norbergite - 12.0; g-AO3 - the rest.
  • the carrier is prepared by the method similar to Example 2, with the difference that the washed and pressed cake is transferred to an autoclave, to which a solution of 14.63 g of boric acid in 1 liter of a 1.5% solution of nitric acid is added. Granulation is carried out through a die, providing particles with a cross section in the form of a circle with a diameter of 1.0 mm The remaining operations and loading of components during preparation of the media are similar to examples 1 and 2. The result is a carrier containing wt.%: Aluminum borate A1zVOB with the structure of norbergite - 25.0; g-AO3 - the rest.
  • the catalyst contains, wt.%: [Co (H20) 2 (SBH507)] 2 [Mo40c (SBH507) 2] - 7.7; Co 2 [H 2 P 2 Mo 5 0 2 s] - 29.0; the carrier is the rest; however, the medium contains May. %: aluminum borate ABBO b with the structure of norbergite - 25.0; g-AO3 - the rest.
  • the catalyst has a specific surface area of 140 m 2 / g, a pore volume of 0.45 cm 3 / g, an average pore diameter of 9 nm, and is a particle with a cross-section in the form of a circle with a diameter of 1.0 mm and a length of up to 20 mm.
  • a catalyst which contains May. %: Mo - 16.0; Co - 4.1; P-1.8; S - 10.7; the carrier is the rest; wherein the carrier contains, wt.%: aluminum borate ABO b with the structure of norbergite - 25.0; g-AO3 - the rest.
  • the carrier is prepared according to a procedure analogous to example 3, with the difference that granulation is carried out through a die, providing particles with a four-leaf cross-section with the diameter described circumference of 1.6 mm.
  • the remaining operations and component loading during preparation of the medium are similar to example 3.
  • the catalyst contains, wt.%: [Co (H20) 2 (SbH507)] 2 [Mo40c (SbH5 (> 7) 2] - 32.0; Co2 [H 2 P2Mo 5 02 s] - 11.1; the carrier is else; the carrier contains, in wt.%: aluminum borate ABO 6 with a norbergite structure - 12.0; g-ABO3 - the rest.
  • the catalyst has a specific surface area of 120 m 2 / g, pore volume 0.35 cm 3 / g, average pore diameter 7 nm, and represents particles with a four-leaf cross-section with a diameter of the circumscribed circle of 1, 6 mm and a length of up to 20 mm.
  • a catalyst which contains wt.%: Mo - 16.0; Co - 4.5; P-0.8; S - 10.8; the carrier is the rest; wherein the carrier contains, wt.%: aluminum borate ABO b with the structure of norbergite - 25.0; g-AO3 - the rest.
  • the proposed catalyst due to its chemical composition has a high desulfurizing and de-nitriding activity, significantly superior to the activity of the prototype catalyst in hydrotreating diesel fuel.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Materials Engineering (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne des catalyseur d'hydroraffinage pour obtenir des produits pétroliers avec une faible teneur en soufre. Elle décrit un catalyseur qui comprend dans sa composition des composés de cobalt, de molybdène, de phosphore, et un vecteur. Le catalyseur comprend, en % en masse: Со(H2O)2(C6H5O7)]2[Mo4O11(C6H5O7)2] - 7,7-32,0; Со2[H2P2Mo5O23] - 11,1-29,0; le vecteur comprenant, en % en masse 5,0-25,0 de borate d'aluminium Аl3ВO6 avec une structure de norbergite; le reste est constitué deAl2O3. Le catalyseur possède une surface spécifique de 120-190 m2/g, un volume de pores 0,35-0,65 см3 /g, un diamètre moyen des pores 7-12 nm et se présente comme des particules ayant une section sous la forme d'un cercle, d'un trilobe ou d'un quadrilobe ayant un diamètre des dimensions décrites plus haut de 1,0-1,6 mm et une longueur jusqu'à 20 mm. Après la sulfuration selon des procédés connus, le catalyseur comprend, en % en masse: Мо - 10,0-16,0; Со - 2,7-4,5; Р- 0,8-1,8; S - 6,7-10,8; le vecteur constituant le reste. Le résultat technique consiste à obtenir un catalyseur possédant une activité dans des réactions cibles qui s'écoulent lors de l'hydropurification de carburant diesel.
PCT/RU2019/000973 2018-12-20 2019-12-18 Catalyseur d'hydropurification de carburant diesel WO2020130881A1 (fr)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
RU2018145235A RU2689735C1 (ru) 2018-12-20 2018-12-20 Катализатор гидроочистки дизельного топлива
RU2018145235 2018-12-20

Publications (1)

Publication Number Publication Date
WO2020130881A1 true WO2020130881A1 (fr) 2020-06-25

Family

ID=67037688

Family Applications (1)

Application Number Title Priority Date Filing Date
PCT/RU2019/000973 WO2020130881A1 (fr) 2018-12-20 2019-12-18 Catalyseur d'hydropurification de carburant diesel

Country Status (2)

Country Link
RU (1) RU2689735C1 (fr)
WO (1) WO2020130881A1 (fr)

Families Citing this family (6)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
RU2716165C1 (ru) * 2019-11-28 2020-03-06 Федеральное государственное бюджетное учреждение науки "Федеральный исследовательский центр "Институт катализа им. Г.К. Борескова Сибирского отделения Российской академии наук" (ИК СО РАН, Институт катализа СО РАН) Способ получения малосернистого дизельного топлива и малосернистого бензина
RU2727144C1 (ru) * 2020-01-17 2020-07-21 Акционерное общество "Газпромнефть - Омский НПЗ" (АО "Газпромнефть - ОНПЗ") Способ приготовления катализатора гидроочистки дизельного топлива
RU2724773C1 (ru) * 2020-01-17 2020-06-25 Акционерное общество "Газпромнефть - Омский НПЗ" (АО "Газпромнефть - ОНПЗ") Катализатор гидроочистки дизельного топлива
RU2722181C1 (ru) * 2020-01-17 2020-05-28 Акционерное общество "Газпромнефть - Омский НПЗ" (АО "Газпромнефть - ОНПЗ") Носитель для катализатора гидроочистки
RU2726634C1 (ru) * 2020-03-19 2020-07-15 Акционерное общество «Газпромнефть - Омский НПЗ» (АО «Газпромнефть - ОНПЗ») Катализатор гидроочистки дизельного топлива
RU2732944C1 (ru) * 2020-03-19 2020-09-24 Акционерное общество «Газпромнефть - Омский НПЗ» (АО «Газпромнефть - ОНПЗ») Способ получения малосернистого дизельного топлива

Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4743574A (en) * 1986-01-09 1988-05-10 Intevep, S.A. Catalyst for hydrotreatment of distillates of petroleum and method for the preparation of same
RU2534998C1 (ru) * 2013-09-27 2014-12-10 Федеральное государственное бюджетное учреждение науки Институт катализа им. Г.К. Борескова Сибирского отделения Российской академии наук Катализатор гидроочистки углеводородного сырья
RU2663902C1 (ru) * 2017-09-25 2018-08-13 Акционерное общество "Газпромнефть - Омский НПЗ" (АО "Газпромнефть - ОНПЗ") Способ гидроочистки углеводородного сырья

Family Cites Families (1)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP4472556B2 (ja) * 2004-03-26 2010-06-02 コスモ石油株式会社 炭化水素油の水素化処理触媒及びその製造方法並びに炭化水素油の水素化処理方法

Patent Citations (3)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4743574A (en) * 1986-01-09 1988-05-10 Intevep, S.A. Catalyst for hydrotreatment of distillates of petroleum and method for the preparation of same
RU2534998C1 (ru) * 2013-09-27 2014-12-10 Федеральное государственное бюджетное учреждение науки Институт катализа им. Г.К. Борескова Сибирского отделения Российской академии наук Катализатор гидроочистки углеводородного сырья
RU2663902C1 (ru) * 2017-09-25 2018-08-13 Акционерное общество "Газпромнефть - Омский НПЗ" (АО "Газпромнефть - ОНПЗ") Способ гидроочистки углеводородного сырья

Also Published As

Publication number Publication date
RU2689735C1 (ru) 2019-05-30

Similar Documents

Publication Publication Date Title
WO2020130881A1 (fr) Catalyseur d'hydropurification de carburant diesel
RU2626398C1 (ru) Катализатор гидроочистки углеводородного сырья
RU2534998C1 (ru) Катализатор гидроочистки углеводородного сырья
JP4275526B2 (ja) 水素化精製触媒、それに用いる担体および製造方法
RU2402380C1 (ru) Катализатор гидроочистки углеводородного сырья, способ его приготовления и процесс гидроочистки
RU2313392C1 (ru) Катализатор гидрообессеривания дизельной фракции и способ его приготовления
RU2726634C1 (ru) Катализатор гидроочистки дизельного топлива
RU2626402C1 (ru) Способ приготовления катализатора гидроочистки сырья гидрокрекинга
RU2629355C1 (ru) Способ получения малосернистого дизельного топлива
RU2691991C1 (ru) Способ получения малосернистого дизельного топлива
RU2663904C1 (ru) Катализатор гидроочистки углеводородного сырья
RU2626399C1 (ru) Способ приготовления катализатора гидроочистки углеводородного сырья
RU2629358C1 (ru) Катализатор гидроочистки сырья гидрокрекинга
RU2732944C1 (ru) Способ получения малосернистого дизельного топлива
RU2726374C1 (ru) Способ приготовления носителя для катализатора гидроочистки
RU2701509C1 (ru) Способ приготовления катализатора гидроочистки дизельного топлива
RU2644563C1 (ru) Катализатор гидроочистки сырья гидрокрекинга
RU2626400C1 (ru) Способ получения малосернистого сырья каталитического крекинга
WO2020130880A1 (fr) Catalyseur de couche de protection pour processus de purification hydraulique de matière première hydrocarbure contenant du silicium
RU2474474C1 (ru) Катализатор, способ его приготовления и способ получения малосернистого дизельного топлива
RU2732243C1 (ru) Способ приготовления катализатора гидроочистки дизельного топлива
RU2724773C1 (ru) Катализатор гидроочистки дизельного топлива
RU2633967C1 (ru) Способ приготовления носителя для катализатора гидроочистки
CN101590416A (zh) 钼镍加氢催化剂及其制备方法
WO2020130874A2 (fr) Catalyseur d'hydroraffinage d'essence obtenue par craquage catalytique

Legal Events

Date Code Title Description
121 Ep: the epo has been informed by wipo that ep was designated in this application

Ref document number: 19899811

Country of ref document: EP

Kind code of ref document: A1

NENP Non-entry into the national phase

Ref country code: DE

122 Ep: pct application non-entry in european phase

Ref document number: 19899811

Country of ref document: EP

Kind code of ref document: A1