WO2019059807A1 - Catalyseur d'hydroraffinage de matière première hydrocarbure - Google Patents

Catalyseur d'hydroraffinage de matière première hydrocarbure Download PDF

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WO2019059807A1
WO2019059807A1 PCT/RU2018/000374 RU2018000374W WO2019059807A1 WO 2019059807 A1 WO2019059807 A1 WO 2019059807A1 RU 2018000374 W RU2018000374 W RU 2018000374W WO 2019059807 A1 WO2019059807 A1 WO 2019059807A1
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catalyst
carrier
boron
rest
norbergite
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PCT/RU2018/000374
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English (en)
Russian (ru)
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Олег Владимирович Климов
Владимир Владимирович ДАНИЛЕВИЧ
Ирина Геннадьевна ДАНИЛОВА
Галина Ивановна КОРЯКИНА
Юлия Витальевна ВАТУТИНА
Игорь Петрович ПРОСВИРИН
Александр Степанович НОСКОВ
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Акционерное Общество "Газпромнефть-Омский Нпз" (Ао "Газпромнефть-Онпз")
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Publication of WO2019059807A1 publication Critical patent/WO2019059807A1/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
    • 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
    • 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
    • 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
    • B01J23/78—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 alkali- or alkaline earth metals

Definitions

  • the invention relates to Hydrotreating catalysts for the production of petroleum products with a low content of sulfur and nitrogen.
  • catalysts containing cobalt and molybdenum oxides supported on alumina are used.
  • So known catalyst [RF Application Mb 2002124681, C10G45 / 08, B01J23 / 887, 16.09.2002], containing in its composition cobalt oxide, molybdenum oxide and aluminum oxide, characterized in that it has the ratio components, May. %: cobalt oxide 3.0-9.0, molybdenum oxide 10.0-24.0 May. %, aluminum oxide else, specific surface 160-250 m 2 / g, mechanical crushing strength 0.6-0.8 kg / mm 2 .
  • the hydrotreating process is carried out at a temperature of 310-340 ° C, pressure 3.0-5.0 MPa, with a ratio hydrogen / feedstock 300-500 Nm 3 / m 3 and a feed space velocity of 1.0-4.0 h ' 1 .
  • the main disadvantage of such a hydrotreating catalyst is the high sulfur content in the resulting products.
  • hydrotreating catalysts use the method of deposition of active metals on an already formed carrier.
  • a carrier aluminum oxide is most often used with a certain size and shape of granules and certain textural characteristics.
  • the carrier is often modified with various additives, including boron compounds.
  • modifying additives are introduced into the carrier either prior to the stage of its formation, by co-precipitating 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 a paste for molding [US N ° 6147432, RF N ° 2472585], or enter the additive by impregnation in a molded carrier, followed by drying and calcining [Catalysis Today 107-108 (2005) 551-558].
  • active metals most often Co, Ni, Mo and W into the catalyst
  • introduction of active metals, most often Co, Ni, Mo and W into the catalyst is carried out by impregnation of the molded carrier with aqueous solutions of their salts.
  • This can be used as a separate application of the active metals by impregnation in several stages [RF N ° N ° 2242501, 2246987], and their application from joint solutions, stabilized by various agents [RF N ° N ° 2073567, 2216404, 2306978].
  • a carrier with improved textural characteristics is used, while the specific surface of the catalyst reaches 300 m g, and the average pore diameter lies in the range of 8-11 nm, which ensures good access of the heteroatomic molecules of the raw material to be converted catalyst centers.
  • a catalyst is known [RF ⁇ ° 2192923, C10G45 / 08, B01J27 / 188, 11.20.2002] based on alumina, which contains, calculated on the weight content of oxide: 2-10 May. % cobalt oxide Soo, 10-30 May. % molybdenum oxide MOOS and 4-10 May. % phosphorus oxide ⁇ 2 0 5 , with a surface area according to the BET method in the range of 100–300 m / g and an average pore diameter in the range of 8–11 nm.
  • the known catalyst contains, in wt.%: Mo - 10.0-14.0; Co - 3.0-4.3; S - 6.7-9.4; carrier - the rest; however, the carrier contains, May. %: aluminum borate A1 3 B0 6 with the structure of norbergite - 5.0-25.0; sodium - not more than 0.03; ⁇ - ⁇ 1 2 0 3 - the rest.
  • the aluminum borate A1 3 B0 6 with the structure of norbergite which is part of the catalyst, consists of particles with sizes from 10 to 200 nm, characterized by interplanar spacings of 3.2 and 2.8 A, with an angle of 53.8 ° between them.
  • the catalyst has a specific surface of 130-180 m 2 / g, a pore volume of 0.35-0.65 cm / g, an average pore diameter of 7-12 nm, and consists of particles with a cross section in the form of a circle, a trefoil or a four leaf clover with a diameter of the circumscribed circle 1.0-1.6 mm and a length of up to 20 mm.
  • the main disadvantage of the known catalyst is that it has a non-optimal chemical composition, which causes its low activity in the reactions of diazotization and desulfurization.
  • the known catalyst contains boron in the form of aluminum borate A1 3 B0 6 with the structure of norbergite, which represents particles with sizes from 10 to 200 nm.
  • borate of aluminum with the structure of norbergite which is formed at the stage of calcining a granular carrier, contributes to obtaining a carrier, the volume and pore size of which provide access to all active hydrocarbon molecules to be converted.
  • borate of aluminum with the structure of norbergite helps to minimize undesirable chemical interaction between the active metals (Co and Mo) and the carrier.
  • An increase in the acidity of the catalyst leads to an increase in its activity, both due to the participation of surface Br ⁇ nsted centers in the catalysis of the diazotization reactions, and due to an increase in the dispersity of sulfide particles and an increase in their activity in desulfurization.
  • the known catalyst has a low acidity and, as a consequence, a relatively low activity in the diazotization and desulfurization.
  • the present invention solves the problem of creating an improved Hydrotreating catalyst, characterized by:
  • the optimal chemical composition of the catalyst which contains boron in the form of two different types of chemical compounds - part of the carrier with a concentration of 5.0-25.0% aluminum borate A1 3 B0 6 with the structure of norbergite, representing particles with sizes from 10 to 200 nm, characterized by interplanar distances of 3.2 and 2.8 A, with an angle between them 53.8 ° and boron with a concentration of 0.4-1.6% in the form surface compounds characterized by absorption bands 930-1040, 1230, 1385-1450 and 3695 cm "1 in the IR spectra.
  • BCCs Bronsted acid centers
  • the technical result is to obtain a catalyst having maximum activity in the target reactions of diazotisation and desulfurization that occur during the hydrotreating of hydrocarbons.
  • a catalyst for Hydrotreating of hydrocarbons which contains, wt%: [Co (H 2 0) 2 (C 6 H 5 0 7 )] 2 [Mo 4 0 1 i (C 6 H 5 0 7 ) 2 ] 33, 0-43.0; boron in the form of surface compounds - 0.4-1.6%, the carrier - the rest; however, the carrier contains, May. %: aluminum borate A1 3 B0 6 with the structure of norbergite - 5.0-25.0; sodium - not more than 0.03; ⁇ - ⁇ 1 2 0 3 - the rest.
  • the catalyst has a specific surface of 130-180 m / g, a pore volume of 0.35-0.65 cm 3 / g, an average pore diameter of 7-12 nm, and consists of particles with a cross section in the form of a circle, trefoil or tetrafole with a diameter of the circumcircle 1.0-1.6 mm and a length of up to 20 mm.
  • a distinctive feature of the proposed catalyst in comparison with the prototype is its chemical composition, namely, that the inventive catalyst contains, May. %: [Co (H 2 0) 2 (C 6 H 5 0 7 )] 2 [Mo 4 O p (C 6 H 5 0 7 ) 2 ] 33.0- 43.0%; boron in the form of surface compounds - 0.4-1.6%, the carrier - the rest; however, the carrier contains, May. %: aluminum borate A1 3 B0 6 with the structure of norbergite - 5.0-25.0; sodium - not more than 0.03; ⁇ - ⁇ 1 2 0 3 - the rest.
  • the output of the content of the catalyst components for the claimed limits leads to a decrease in the activity of the catalyst.
  • An increase in the boron content in the form of surface compounds of more than 1.6% is unattainable due to the limited solubility of boric acid in water.
  • the second distinguishing feature of the proposed catalyst in comparison with the prototype is that it contains dispersed surface boron compounds, characterized by absorption bands 930-1040, 1230, 1385-1450 and 3695 cm -1 in the IR spectra.
  • the fourth distinguishing feature of the proposed catalyst compared with the prototype is that after sulfiding it has a dispersion of supported metals, determined according to XPS data of the intensity of IMo3d / IA12p lines in the interval 1.45-1.55, and by the ratio of intensities of 1 ⁇ réelle2 counter / 1 ⁇ 12 license lines in the range of 1.14-1.18.
  • the technical result consists of the following components: 1.
  • the claimed chemical composition of the catalyst determines the maximum activity in the target reactions of deazorization and desulfurization occurring during the hydrotreatment of hydrocarbon raw materials.
  • the presence of boron catalyst in the form of two different types chemical compounds - part of the carrier with a concentration of 5.0–25.0% aluminum borate A1 3 B0 6 with the structure of norbergite, and boron with a concentration of 0.4–1.6% in the form of surface compounds, provides an optimal combination of textural and acidic characteristics of the carrier and catalyst.
  • the presence of boron in the catalyst composition with a concentration of 0.4-1.6% in the form of surface compounds, characterized by absorption bands by absorption bands 930-1040, 1230, 1385-1450 and 3695 cm "1 in the IR spectra, provides a catalyst that after sulphidation, it has a dispersion of deposited metals, determined according to XPS data by the ratio of the intensities of the IMo3d / IA12p lines in the interval of 1.45-1.55, and by the ratio of the intensities of the 1Co2p / 1A12p lines in the interval of 1.14-1.18. increased activity of the sulfide component in target reactions of desulfurization and diazotization.
  • PTH thermal activation of hydrargillite
  • mass fraction of X-ray amorphous phase %, not less than 80
  • proportion of mass loss during calcination at (900 ⁇ 20) ° ⁇ ,% - 10-12 specific surface, m / g, not less than 120; total pore volume (capacity), cm / 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 ground in a planetary mill to particles with an average size of 20 microns.
  • a portion of the crushed powder is hydrated with stirring for 2 hours in low-concentrated solutions of nitric acid heated to 50 ° C (acid module 0.03). After that, the resulting suspension is filtered under vacuum and repeatedly washed with distilled water. The result is a wet sediment.
  • Hydrothermal treatment of the washed precipitate is carried out in an autoclave in aqueous solutions of nitric acid with the addition of a specified 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 discharged, and the contents of the vessel are repulped with distilled water until a suspension is suitable for spray drying. Next, carry out the drying in a spray dryer at an air temperature at the entrance to the dryer 280 ° C and continuous stirring of the suspension. The finished boron-containing aluminum hydroxide powder is discharged from the glass of the spray dryer cyclone dust collector.
  • the ammonia solution is prepared in such a way that the amount of ammonia aqueous 25% is 1.5 ml per 40 g of powder after spray drying.
  • the finished plastic mass is transferred from the mixer to the molding cylinder of the laboratory extruder and is forced through the die hole, providing extrudates finished media with a cross-section in the shape of a circle, trefoil or chetyrehlistnik with size from the top of the trefoil to the middle of the base from 1.0 to 1.6 mm.
  • the extrudates are dried in a drying oven at a temperature of (110 ⁇ 10) ° C for 2 hours. Heat treatment is carried out in a muffle furnace with compressed air fed into the furnace. The extrudates in a porcelain dish are placed in an oven and calcined at a temperature of (550 ⁇ 10) ° C for 4 hours.
  • Ready media contains May. %: aluminum borate A1 3 B0 6 with the structure of norbergite - 5.0-25.0; sodium - not more than 0.03; ⁇ - ⁇ 1 2 0 3 - the rest, and has a specific surface of 200-280 m / g, a pore volume of 0.6-0.8 cm / 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 chetyrehlistnika with a diameter of the circumscribed circle 1.0-1.6 mm and a length of up to 20 mm.
  • the aluminum borate A1 3 B0 6 with the structure of norbergite, which is part of the carrier, consists of particles with sizes from 10 to 200 nm, characterized by interplanar distances of 3.2 and 2.8 A, with an angle of 53.8 ° between them.
  • Stirring is continued at (65-70) ° C until a homogeneous transparent solution of dark cherry color, not containing turbidity, bubbles and foam.
  • the solution contains cobalt and molybdenum in the form of a bimetallic complex compound [Co (H 2 0) 2 (C 6 H 5 0 7 )] 2 [Mo 4 0 11 (C 6 H 5 0 7 ) 2 ].
  • boric acid H3BO3 is added in an amount to obtain a catalyst containing 0.4-1.6% boron in the form of surface compounds, stirring is continued until complete dissolution of boric acid.
  • the prepared solution is poured into a calibrated measuring cylinder, after which the volume of the solution is adjusted to the specified amount by adding distilled water.
  • the resulting solution is impregnated with boron-containing carrier, using either the impregnation of the carrier according to moisture capacity, or from an excess of solution.
  • the impregnation is carried out at a temperature of 15-90 ° C for 5-60 minutes with occasional stirring, in the case of impregnation from the excess solution after impregnation, the 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 100-200 ° C.
  • the catalyst contains, in wt.%: Mo - 10.0-14.0; Co - 3.0-4.3; S - 6.7-9.4; boron in the form of surface compounds - 0.5-2.0; carrier - the rest; however, the carrier contains, May. %: aluminum borate A1 3 B0 6 with the structure of norbergite - 5.0-25.0; sodium - not more than 0.03; ⁇ - ⁇ 1 2 0 3 - the rest.
  • the carrier for which 150 g of the product of thermal activation of hydrargillite is ground in a planetary mill to particles in the range of 20-50 microns.
  • the powder is hydrated with stirring and heated 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 until the residual sodium content in the powder is not more than 0.03%.
  • the washed and pressed pellet is transferred to an autoclave, to which is added a solution of 2.3 g of boric acid in 1 liter of a 1.5% aqueous solution of nitric acid, having a pH of 1.4.
  • the autoclave is heated to 150 ° C and held for 12 hours.
  • the autoclave is cooled to room temperature and the resulting suspension is dried on a spray dryer at air inlet to the dryer 155 ° C and the suspension is continuously stirred, and the dried powder is collected in the receiving container of the dryer.
  • a weighed 150 g of powder is placed in a mixer trough with ⁇ -shaped blades, peptized with 2.5% aqueous ammonia solution, and then extruded at a pressure of 60.0 MPa, through a spinneret, providing particles with a trefoil cross-section with a diameter of circumscribed 1.6 mm. Molded 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 A1 3 B0 6 with the structure of norbergite - 5.0; sodium - 0.03; ⁇ - ⁇ 1 2 0 3 - the rest.
  • the catalyst contains, may. %: [Co (H 2 0) 2 (C 6 H 5 0 7 )] 2 [Mo 4 Ots (C 6 H 5 0 7 ) 2 ] 38.4%; carrier - the rest; however, the carrier contains, May. %: aluminum borate A1 3 B0 6 with the structure of norbergite - 5.0; sodium - 0.03; ⁇ - ⁇ 1 2 0 3 - the rest.
  • the catalyst has a specific surface of 150 m 2 / g, a pore volume of 0.55 cm 3 / g, an average pore diameter of 13 nm, and consists of particles with a trefoil-shaped cross-section with a diameter of 1.6 mm and a length of 20 mm.
  • the aluminum borate catalyst A1 3 B0 6 with the structure of norbergite, which is a part, consists of particles with sizes from 10 to 200 nm, characterized by interplanar spacings of 3.2 and 2.8 A, with an angle of 53.8 ° between them.
  • the catalyst contains particles of aluminum borate A1 3 B0 6 with the structure of norbergite with sizes from 10 to 200 nm, characterized by interplanar spacings of 3.2 and 2.8 A, with an angle of 53.8 ° between them.
  • the catalyst is sulfided by one of the known methods.
  • the result is a catalyst that contains, may. %: Mo - 12.5; Co — 3.85; S - 8.3; carrier - the rest; however, the carrier contains, May. %: aluminum borate A1 3 B0 6 with the structure of norbergite - 5.0; sodium - 0.03; ⁇ - ⁇ 1 2 0 3 - the rest.
  • the catalyst is characterized by the method of x-ray photoelectron spectroscopy (XPS).
  • the IMo3d / IA12p and 1Co2p / 1A12p surface atomic ratios were calculated using VG Eclipse software after processing the non-linear Shirley background and the contribution of the S2 s signal to Mo3d. Data on the dispersion of Mo and Co are given in Table 2.
  • the catalyst is tested in hydrotreatment of diesel fuel containing 0.37% sulfur, 250 ppm of nitrogen, having a density of 0.86 g / cm 3 , a boiling range of 210-360 ° C, T 5 - 356 ° C.
  • the catalyst is also tested in the hydrotreatment of vacuum gas oil.
  • Hydrotreating of vacuum gas oil (2.5% sulfur, 1500 ppm of nitrogen, kk 560 ° C) is carried out at 375 ° C, pressure of 7.0 MPa, mass flow rate of vacuum gas oil 0.85 h "1 , volume ratio hydrogen / raw material 500
  • a carrier containing may. %: aluminum borate A1 3 B0 6 with the structure of norbergite - 5.0; sodium - 0.03; ⁇ - ⁇ 1 2 0 3 - the rest.
  • the temperature of the solution is raised to 90 ° ⁇ and dissolve in it 44.63 g of boric acid H 3 B0 3 . After complete dissolution of all components, the solution is adjusted to 200 ml by adding distilled water heated to 90 ° C.
  • the catalyst contains, may. %: [Co (H 2 0) 2 (C 6 H 5 0 7 )] 2 [Mo 4 Op (C 6 H 5 0 7 ) 2 ] - 38.4; boron in the form of surface compounds - 1.6, the carrier - the rest; however, the carrier contains, May. %: aluminum borate A1 3 B0 6 with the structure of norbergite - 5.0; sodium - 0.03; ⁇ - ⁇ 1 2 0 3 - the rest.
  • the catalyst has a specific surface of 145 m / g, a pore volume of 0.50 cm / g, an average pore diameter of 13 nm, and consists of particles with a trefoil-shaped cross-section with a circumferential diameter of 1.6 mm and a length of up to 20 mm.
  • the aluminum borate A1 3 B0 6 with the structure of norbergite, which is part of the catalyst, consists of particles with sizes from 10 to 200 nm, characterized by interplanar distances of 3.2 and 2.8 A, with an angle of 53.8 ° between them.
  • the catalyst is sulfided similarly to example 1.
  • the result is a catalyst that contains, may. %: Mo - 12.5; Co — 3.85; S - 8.3; boron in the form of surface compounds - 2.0, the carrier - the rest; however, the carrier contains, May. %: aluminum borate A1 3 B0 6 with the structure of norbergite - 5.0; sodium - 0.03; ⁇ - ⁇ 1 2 0 3 - the rest.
  • the catalyst is characterized by the method of x-ray photoelectron spectroscopy (XPS), analogously to example 1. Data on the dispersion of Mo and Co are given in table 2.
  • XPS x-ray photoelectron spectroscopy
  • the catalyst is tested in the hydrotreatment of diesel fuel and vacuum gas oil as in Example 1.
  • the results of testing the catalyst in hydrotreating are shown in Table 3.
  • 100 g of the obtained carrier is impregnated at 70 ° C according to the moisture capacity of 67 ml of a solution of a bimetallic complex compound [Co (H20) 2 (C 6 H 5 0 7 )] 2 [Mo 4 0 11 (C 6 H 5 0 7 ) 2 ] and boric acid. Then the catalyst is dried in air at 100 ° C.
  • the catalyst contains, may. %: [Co (H 2 0) 2 (C 6 H 5 0 7 )] 2 [Mo 4 Ots (C 6 H 5 0 7 ) 2 ]
  • the catalyst is characterized by the methods of IR-spectroscopy and HRTD similarly to example 1. The data of IR-spectroscopy are shown in table 1.
  • the catalyst is sulfided similarly to example 1.
  • the result is a catalyst, which contains May. %: Mo - 12.5; Co — 3.85; S - 8.3; boron in the form of surface compounds - 1.0; carrier - the rest; however, the carrier contains, May. %: aluminum borate A1 3 B0 6 with the structure of norbergite
  • the catalyst is characterized by the method of x-ray photoelectron spectroscopy (XPS), analogously to example 1. Data on the dispersion of Mo and Co are given in table 2.
  • XPS x-ray photoelectron spectroscopy
  • the result is a carrier containing May. %: aluminum borate A1 3 B0 6 with the structure of norbergite - 25.0; sodium - 0.023; ⁇ - ⁇ 1 2 0 3 - the rest.
  • 100 g of the obtained carrier is impregnated with a capacity of 67 ml of a solution of a bimetallic complex compound.
  • the catalyst contains, may. %: [Co (H 2 0) 2 (C 6 H 0 7 )] 2 [Mo40ii (C 6 H 5 07) 2]
  • the catalyst is characterized by the methods of IR-spectroscopy and HRTD similarly to example 1. The data of IR-spectroscopy are shown in table 1.
  • the catalyst has a specific surface of 180 m 2 / g, a pore volume of 0.55 cm 3 / g, an average pore diameter of 7 nm, and consists of particles with a trefoil-shaped cross-section with a diameter of 1.6 mm and a length of 20 mm.
  • the aluminum borate A1 3 B0 6 with the structure of norbergite, which is part of the catalyst, consists of particles with sizes from 10 to 200 nm, characterized by interplanar distances of 3.2 and 2.8 A, with an angle of 53.8 ° between them.
  • the catalyst is sulfided similarly to example 1.
  • the result is a catalyst, which contains May. %: Mo - 12.5; Co — 3.85; S - 8.3; boron in the form of surface compounds - 1.0; carrier - the rest; however, the carrier contains, May. %: aluminum borate A1 3 B0 6 with the structure of norbergite - 25.0; sodium - 0.023; ⁇ - ⁇ 1 2 0 3 - the rest.
  • the catalyst is characterized by the method of x-ray photoelectron spectroscopy (XPS), analogously to example 1. Data on the dispersion of Mo and Co are given in table 2.
  • XPS x-ray photoelectron spectroscopy
  • a solution of the bimetallic complex compound [Co (H 2 0) 2 (C 6 H 5 0 7 )] 2 [Mo 4 Oz (C b H 5 0 7 ) 2 ] is prepared, for which, in 100 ml of distilled water, the solution is sequentially dissolved with stirring 63 , 27 g of citric acid With 6 H 8 0 7 ; 77.58 g of ammonium paramolybdate ( ⁇ 4 ) 6 ⁇ 7 0 24 ⁇ 4 ⁇ 2 0, 26.0 g of cobalt (II) carbonate basic aqueous CoC0 3 " tCO (OH) 2 " pN 2 0 and 11.16 g of boric acid H 3 V 3 . After complete dissolution of all components, the solution is made up to 200 ml by adding distilled water.
  • the catalyst contains, may. %: [Co (H 2 0) 2 (C 6 H 5 0 7 )] 2 [Mo Op (C 6 H 5 0 7 ) 2 ] - 32.7; boron in the form of surface compounds - 0.4; carrier - the rest; however, the carrier contains, May. %: aluminum borate A1 3 B0 6 with the structure of norbergite - 12.0; sodium - 0.028; ⁇ - ⁇ 1 2 0 3 - the rest.
  • the catalyst is characterized by the methods of IR-spectroscopy and HRTD similarly to example 1. The data of IR-spectroscopy are shown in table 1.
  • 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 14 nm, and is a trefoil-shaped particle with a circumferential diameter of 1, 6 mm and a length of up to 20 mm.
  • the aluminum borate A1 3 B0 6 with the structure of norbergite, which is part of the catalyst, consists of particles with sizes from 10 to 200 nm, characterized by interplanar distances of 3.2 and 2.8 A, with an angle of 53.8 ° between them.
  • the catalyst is sulfided similarly to example 1.
  • the result is a catalyst that contains, may. %: Mo - 10.0; Co - 3.0; S — 6.7; boron in the form of surface compounds - 0.5; carrier - the rest; however, the carrier contains, May. %: aluminum borate A1 3 B0 6 with the structure of norbergite - 12.0; sodium - 0.028; ⁇ - ⁇ 1 2 0 3 - the rest.
  • the catalyst is characterized by the method of x-ray photoelectron spectroscopy (XPS), analogously to example 1. Data on the dispersion of Mo and Co are given in table 2.
  • XPS x-ray photoelectron spectroscopy
  • the catalyst contains, may. %: [Co (H 2 0) 2 (C 6 H 5 0 7 )] 2 [Mo 4 Op (C 6 H 5 0 7 ) 2 ] -
  • the catalyst has a specific surface of 130 m / g, a pore volume of 0.35 cm / g, an average pore diameter of 10 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.
  • the aluminum borate A1 3 B0 6 with the structure of norbergite, which is part of the catalyst, consists of particles with sizes from 10 to 200 nm, characterized by interplanar distances of 3.2 and 2.8 A, with an angle of 53.8 ° between them.
  • the catalyst is sulfided similarly to example 1.
  • the result is a catalyst that contains, may. %: Mo - 14.0; Co — 4.3; S — 9.4; boron in the form of surface compounds - 2.0; carrier - the rest; however, the carrier contains, May. %: aluminum borate A1 3 B0 6 with the structure of norbergite - 12.0; sodium - 0.028; ⁇ - ⁇ 1 2 0 3 - the rest.
  • the catalyst is characterized by the method of x-ray photoelectron spectroscopy (XPS), analogously to example 1. Data on the dispersion of Mo and Co are given in table 2. Next, carry out the Hydrotreating of hydrocarbons as in example 1. The results of testing the catalyst in Hydrotreating are shown in table 3.
  • XPS x-ray photoelectron spectroscopy
  • the resulting catalyst contains, may. %:
  • the catalyst has a specific surface of 175 m / g, a pore volume of 0.6 cm / g, an average pore diameter of 14 nm, and is a particle with a cross section in the form of a four-leaf with a circumferential diameter of 1.6 mm and a length of 20 mm.
  • the aluminum borate A1 3 B0 6 with the structure of norbergite, which is part of the catalyst, consists of particles with sizes from 10 to 200 nm, characterized by interplanar distances of 3.2 and 2.8 A, with an angle of 53.8 ° between them.
  • the catalyst is sulfided similarly to example 1.
  • the result is a catalyst, which contains May. %: Mo - 11.7; Co — 3.6; S - 7.9; boron in the form of surface compounds - 0.5; carrier - the rest; wherein media contains, may. %: aluminum borate A1 3 B0 6 with the structure of norbergite - 12.0; sodium - 0.028; ⁇ - ⁇ 1 2 0 3 - the rest.
  • the catalyst is characterized by the method of x-ray photoelectron spectroscopy (XPS), analogously to example 1. Data on the dispersion of Mo and Co are given in table 2.
  • XPS x-ray photoelectron spectroscopy
  • the proposed catalyst due to its chemical composition, dispersion of the active component, texture and acidity, has a high activity, significantly exceeding the activity of the prototype catalyst in the desulfurization and diazotization of hydrocarbon raw materials.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Materials Engineering (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Catalysts (AREA)

Abstract

L'invention concerne des catalyseurs d'hydroraffinage de matières première hydrocarbures. L'invention porte sur un catalyseur qui comprend, en % en poids: [Co(H2O)2(C6H5O7)]2[Mo4O11(C6H5O7)2]: 33,0-43,0; bore sous forme de de composés de surface: 0,4-1,6; le reste consistant en une matière de charge; la matière de charge comprend, en % en poids: du borate d'aluminium Аl3ВO6 ayant une structure de Norbergite; 5,0-25,0; sodium: pas plus de 0,03; le reste se composant de γ-Αl2O3. Le borate d'aluminium Аl3ВO6 possédant une structure de Norbergite se présente sous forme de particules avec une taille allant de 10 à 200 nm caractérisées par des distances entre les plans de 3,2 à 2,8 A, et un angle de 53,8° entre eux. Le bore sous forme de composés de surface est caractérisé par des bandes d'absorption de 930-1040, 1230, 1385-1450 et 3695cm-1 dans les spectres infrarouges. Le catalyseur comprend des sites acides de Brönsted forts et des sites acides de Brönsted de force moyenne. Après la sulfuration, le catalyseur contient, en % en poids: Мо - 10,0-14,0; Со - 3,0-4,3; S - 6,7-9,4; vore sous forme de composés de surface: 0,5 - 2,0; le reste consistant en une matière de charge. La dispersivité des métaux apportés déterminée selon les données de spectroscopie photoélectronique X par rapport aux lignes d'intensités IMo3d/IA12p se situe dans une plage de 1,45-1,5 et, par rapport aux lignes d'intensités 1Со2р/1А12p, dans une plage de 1,14-1,18.
PCT/RU2018/000374 2017-09-25 2018-06-07 Catalyseur d'hydroraffinage de matière première hydrocarbure WO2019059807A1 (fr)

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Cited By (3)

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Publication number Priority date Publication date Assignee Title
WO2021127765A1 (fr) * 2019-12-27 2021-07-01 Petróleo Brasileiro S.A. - Petrobras Méthode d'obtention d'un support pour catalyseurs d'hydrotraitement, support de catalyseurs d'hydrotraitement, catalyseurs d'hydrotraitement, procédé d'obtention de catalyseurs d'hydrotraitement et utilisation du support sur des catalyseurs d'hydrotraitement
WO2021229334A1 (fr) 2020-05-15 2021-11-18 nChain Holdings Limited Systèmes et procédés informatisés de traitement, d'accès et de transmission de données efficaces et sécurisés par l'intermédiaire d'une chaîne de blocs
WO2024052319A1 (fr) 2022-09-09 2024-03-14 Nchain Licensing Ag Procédés et systèmes mis en œuvre par ordinateur pour améliorer les communications à travers un réseau de chaînes de blocs

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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
RU2008972C1 (ru) * 1992-08-14 1994-03-15 Всероссийский научно-исследовательский институт по переработке нефти Способ приготовления катализатора для гидроочистки нефтяных фракций
RU2626398C1 (ru) * 2016-11-09 2017-07-27 Акционерное общество "Газпромнефть - Омский НПЗ" (АО "Газпромнефть - ОНПЗ") Катализатор гидроочистки углеводородного сырья
RU2629355C1 (ru) * 2016-11-09 2017-08-29 Акционерное общество "Газпромнефть - Омский НПЗ" (АО "Газпромнефть - ОНПЗ") Способ получения малосернистого дизельного топлива

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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
RU2008972C1 (ru) * 1992-08-14 1994-03-15 Всероссийский научно-исследовательский институт по переработке нефти Способ приготовления катализатора для гидроочистки нефтяных фракций
RU2626398C1 (ru) * 2016-11-09 2017-07-27 Акционерное общество "Газпромнефть - Омский НПЗ" (АО "Газпромнефть - ОНПЗ") Катализатор гидроочистки углеводородного сырья
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Cited By (4)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
WO2021127765A1 (fr) * 2019-12-27 2021-07-01 Petróleo Brasileiro S.A. - Petrobras Méthode d'obtention d'un support pour catalyseurs d'hydrotraitement, support de catalyseurs d'hydrotraitement, catalyseurs d'hydrotraitement, procédé d'obtention de catalyseurs d'hydrotraitement et utilisation du support sur des catalyseurs d'hydrotraitement
WO2021229334A1 (fr) 2020-05-15 2021-11-18 nChain Holdings Limited Systèmes et procédés informatisés de traitement, d'accès et de transmission de données efficaces et sécurisés par l'intermédiaire d'une chaîne de blocs
WO2024052319A1 (fr) 2022-09-09 2024-03-14 Nchain Licensing Ag Procédés et systèmes mis en œuvre par ordinateur pour améliorer les communications à travers un réseau de chaînes de blocs
WO2024052398A1 (fr) 2022-09-09 2024-03-14 Nchain Licensing Ag Procédés et systèmes mis en œuvre par ordinateur pour des communications améliorées à travers un réseau de chaîne de blocs

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