WO2022209410A1 - Catalyseur d'hydrotraitement pour huile hydrocarbonée et son procédé de production - Google Patents

Catalyseur d'hydrotraitement pour huile hydrocarbonée et son procédé de production Download PDF

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WO2022209410A1
WO2022209410A1 PCT/JP2022/006712 JP2022006712W WO2022209410A1 WO 2022209410 A1 WO2022209410 A1 WO 2022209410A1 JP 2022006712 W JP2022006712 W JP 2022006712W WO 2022209410 A1 WO2022209410 A1 WO 2022209410A1
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inorganic oxide
catalyst
hydrotreating catalyst
carrier
metal component
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PCT/JP2022/006712
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English (en)
Japanese (ja)
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和成 田川
泰 新宅
雄介 松元
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日揮触媒化成株式会社
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Publication of WO2022209410A1 publication Critical patent/WO2022209410A1/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
    • 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
    • B01J27/195—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium with vanadium, niobium or tantalum
    • B01J27/198—Vanadium
    • B01J27/199—Vanadium with chromium, molybdenum, tungsten or polonium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/04—Mixing
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • C—CHEMISTRY; METALLURGY
    • 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 present invention relates to a hydrotreating catalyst for removing sulfur, metal, and silicon in hydrocarbon oil in the presence of hydrogen, and a method for producing the same.
  • the reaction proceeds at high temperature and high pressure using a catalyst, but since the economic efficiency of the process is improved by lowering the reaction conditions at low temperature and pressure, it is desirable that the catalyst has high activity. It is rare.
  • the hydrotreating catalyst is prepared by impregnating a carrier made of inorganic oxides such as alumina with an impregnating solution containing molybdenum and cobalt or nickel, which are active metals, and drying and calcining the carrier.
  • a carrier made of inorganic oxides such as alumina with an impregnating solution containing molybdenum and cobalt or nickel, which are active metals, and drying and calcining the carrier.
  • the metal supported on the catalyst is sulfurized with a sulfur compound and reacted with the hydrocarbon oil at high temperature to remove sulfur and metal at the same time as hydrogenation.
  • silicon contained in antifoaming agents and the like used in the process from extraction of crude oil to the hydrotreating process deposits on the catalyst surface and deactivates the catalyst in the hydrotreating process, so its removal is required.
  • Patent Document 1 Conventionally, various studies have been made on the shape and pore structure of the catalyst in order to improve the performance of the hydrotreating catalyst (for example, Patent Document 1).
  • Patent Document 1 In addition, in the paper entitled " Hydrodesulfurization Activity of Catalysts with Non-Cylindrical Shape" in Non-Patent Document 1, it is stated that the hydrodesulfurization activity and the surface of the catalyst are highly correlated. It can be said that the improvement of the geometric surface ratio by is effective for improving the activity.
  • an object of the present invention is to provide a catalyst with improved performance in the hydrotreating of hydrocarbon oil.
  • the present invention relates to, for example, the following [1] to [9].
  • [1] comprising an inorganic oxide support and an active metal component supported on said inorganic oxide support; the active metal component comprises a first metal that is at least one of molybdenum and tungsten and a second metal that is at least one of cobalt and nickel;
  • a hydrotreating catalyst for hydrocarbon oils that satisfies the following requirements (1) to (3) in the Log differential pore volume distribution measured by mercury porosimetry.
  • Requirement (2): dV/d (log D) is maximized in the pore diameter range of 2-50 ⁇ m.
  • Requirement (3) The ratio of the pore volume with a pore diameter of 2 to 50 ⁇ m to the total pore volume is 3% or more.
  • [6] comprising an inorganic oxide support and an active metal component supported on said inorganic oxide support;
  • the active metal component comprises a first metal that is at least one of molybdenum and tungsten and a second metal that is at least one of cobalt and nickel;
  • 3 crevasses/mm 2 or more having a maximum width of 2 ⁇ m or more and a length of 100 ⁇ m or more are present on the surface of the inorganic oxide support,
  • a hydrotreating catalyst for hydrocarbon oils that satisfies the following requirement (1) in the Log differential pore volume distribution measured by mercury porosimetry. Requirement (1): dV/d (log D) is maximized in the pore diameter range of 5-30 nm.
  • the hydrotreating catalyst for hydrocarbon oil of the present invention is excellent in hydrodesulfurization activity, hydrodemetalization ability, and silicon trapping ability. Further, according to the method for producing a hydrotreating catalyst for hydrocarbon oil of the present invention, a hydrotreating catalyst for hydrocarbon oil having excellent hydrodesulfurization activity, hydrodemetalization ability, and silicon trapping ability is produced. be able to.
  • Pore distribution of the catalysts of Example 1 and Comparative Example 1 measured by mercury porosimetry Enlarged view of pore size distribution of the catalysts of Example 1 and Comparative Example 1 measured by mercury porosimetry Photomicrograph of the catalyst of Example 1
  • the hydrotreating catalyst for hydrocarbon oil according to the present invention contains an inorganic oxide support and an active metal component supported on the inorganic oxide support, and mercury It is characterized in that requirements (1) to (3), which will be described later, are satisfied in the pore size distribution measured by the indentation method.
  • Inorganic oxides constituting the carrier include oxides or composite oxides of aluminum, silicon, titanium, boron, zirconium, cerium or phosphorus. Specific examples include alumina, silica, titania, boria and zirconia.
  • ceria phosphorous oxide, silica-alumina, alumina-titania, alumina-zirconia, alumina-boria, phosphorous oxide-alumina, silica-alumina-boria, phosphorous oxide-alumina-boria, phosphorous oxide-alumina-silica , silica-alumina-titania, and silica-alumina-zirconia, preferably alumina or a composite oxide of aluminum containing alumina as a main component and other elements. These may be used singly or in combination of two or more.
  • the inorganic oxide carrier contains a matrix component made of the inorganic oxide and inorganic fibers, for example, when produced by the production method described below.
  • the content of the inorganic fibers in the inorganic oxide support is preferably 0.2 to 10% by mass, more preferably 0.5 to 5% by mass.
  • an active metal component is supported on the inorganic composite oxide support.
  • the active metal component includes, as active metal species, a first metal that is at least one of molybdenum and tungsten, and a second metal that is at least one of cobalt and nickel. Accordingly, an active metal component including, for example, molybdenum as a first metal and cobalt as a second metal is supported on the support. Active metal components include oxides comprising a first metal and a second metal.
  • the first metal may be molybdenum, tungsten, or both molybdenum and tungsten, preferably molybdenum.
  • the content (supported amount) of the first metal component in the catalyst of the present invention can be appropriately changed depending on the properties of the feedstock to be treated. 30% by mass, preferably 15 to 22% by mass.
  • the catalyst of the present invention exhibits good desulfurization activity.
  • the content of the first metal is equal to or less than the upper limit, aggregation of the first metal can be prevented and good dispersibility can be obtained.
  • the second metal may be cobalt, nickel, or both cobalt and nickel.
  • the content (supported amount) of the second metal component in the catalyst of the present invention can be appropriately changed depending on the properties of the feedstock to be treated. ⁇ 10.0% by mass, preferably 2.0 to 8.0% by mass.
  • the second metal acts as a promoter for the first metal.
  • the content of the second metal is equal to or higher than the lower limit, the first metal and the second metal, which are active metal species, can maintain an appropriate structure.
  • the hydrotreating catalyst of the present invention may contain carbon, phosphorus, boron, etc. derived from organic acids that may be used in the production process.
  • the hydrotreating catalyst of the present invention contains an inorganic oxide support and an active metal component supported on the inorganic oxide support, and is processed by a mercury intrusion method (contact angle of mercury: 130°, surface tension: 480 dyn/cm).
  • the measured Log differential pore volume distribution satisfies the following requirements (1) to (3).
  • Requirement (1) expresses that the hydrotreating catalyst of the present invention has mesopores like a typical hydrotreating catalyst.
  • Requirement (2) expresses that the hydrotreating catalyst of the present invention has characteristic crevasses on its surface as shown in FIG.
  • a peak (maximum point) of dV/d (log D) exists in a range of pore diameters of 2 ⁇ m (2000 nm) or more, the hydrotreating catalyst has excellent hydrodesulfurization activity, hydrodemetalization ability, and silicon trapping ability. .
  • the peak (maximum point) of dV/d (log D) exists in the range of pore diameters of 50 ⁇ m (50000 nm) or less, the hydrotreating catalyst has high strength.
  • the value of this peak (maximum point) is, for example, 0.02 cc/g or more.
  • Requirement (3) expresses that the volume of the pores due to the crevasses occupies a constant ratio with respect to the pore volume of the entire hydrotreating catalyst. Since the hydrotreating catalyst of the present invention has crevices represented by the requirements (2) and (3), the catalyst volume surface ratio is dramatically improved compared to the conventional technology, and the hydrodesulfurization activity , demetallization ability, silicon trapping ability, etc., which are correlated with the surface of the catalyst, are improved.
  • the presence of many crevasses in the catalyst can be expected to significantly improve the catalyst volume surface ratio compared to changing the size and shape of the molded body, and has macropores formed by adding organic additives. It can be expected that the diffusibility of the reaction oil to the inside of the catalyst is better than that of the catalyst.
  • the surface of the inorganic oxide carrier (the surface facing the direction perpendicular to the extrusion direction when the carrier is produced by extrusion molding) preferably has a crevasse having a maximum width of 2 ⁇ m or more and a length of 100 ⁇ m or more. is 3 crevasses/mm 2 or more, more preferably 5 crevasses/mm 2 or more (the upper limit is, for example, 50 crevasses/mm 2 ) having a maximum width of 10 ⁇ m or more and a length of 100 ⁇ m or more. These values can be measured based on SEM images of the hydroprocessing catalyst.
  • the hydrotreating catalyst of the present invention has a crushing strength of usually 5 N/mm or more, preferably 8 N/mm or more, more preferably 10 N/mm or more, as measured by the method described below. When the crushing strength is within this range, it is possible to prevent the catalyst from breaking during filling and causing drift or pressure loss during the reaction.
  • Another aspect of the hydrotreating catalyst of the present invention is comprising an inorganic oxide support and an active metal component supported on said inorganic oxide support; the active metal component comprises a first metal that is at least one of molybdenum and tungsten and a second metal that is at least one of cobalt and nickel; 3 crevasses/mm 2 or more having a maximum width of 2 ⁇ m or more and a length of 100 ⁇ m or more are present on the surface of the inorganic oxide support,
  • the hydrotreating catalyst for hydrocarbon oil satisfies the above requirement (1) in terms of log differential pore volume distribution measured by mercury porosimetry.
  • the method for producing a hydrotreating catalyst for hydrocarbon oil of the present invention comprises: (1) mixing an inorganic oxide or a precursor of the inorganic oxide with an inorganic fiber to prepare a carrier material mixture; (2) a step of obtaining a molded product by extrusion molding from the carrier raw material mixture; (3) a step of drying and calcining the molded product to obtain an inorganic oxide carrier; (4) preparing an impregnating solution containing a raw material for a first metal component that is at least one of molybdenum and tungsten, a raw material for a second metal component that is at least one of cobalt and nickel, and a solvent; A step of contacting the impregnating solution with the inorganic oxide support to obtain a support, and (5) a step of heat-treating the support to obtain a hydrotreating catalyst.
  • Step (1) is a step of mixing inorganic oxides or precursors thereof with inorganic fibers to prepare a mixture of carrier raw materials.
  • An inorganic oxide precursor can be manufactured by a conventionally well-known method. An example is given below. First, a basic metal salt aqueous solution and an acidic metal salt aqueous solution are mixed to obtain a slurry of an inorganic oxide precursor (hydrate).
  • basic aluminum salts sodium aluminate, potassium aluminate and the like are preferably used.
  • acidic aluminum salt aluminum sulfate, aluminum chloride, aluminum nitrate and the like are preferably used.
  • the silica source includes an aqueous solution of sodium silicate and a hydrogel of sodium silicate as an alkali silicate
  • the phosphate source includes phosphite ions such as ammonium phosphate, potassium phosphate, Phosphate compounds that generate phosphate ions in water, such as sodium phosphate, phosphoric acid, and phosphorous acid, can be used.
  • titanium mineral salts include titanium tetrachloride, titanium trichloride, titanium sulfate, titanyl sulfate, and titanium nitrate. Titanium sulfate and titanyl sulfate are particularly preferred because they are inexpensive.
  • the slurry is washed with warm water, for example, an ammonia aqueous solution with a concentration of 0.3% by mass. Then, ion-exchanged water is added to the cake-like slurry after washing to form a slurry, and an aging process is performed. In the aging step, for example, an aqueous organic acid solution, aqueous ammonia, etc. are added to the obtained slurry to adjust the pH to, for example, 9.5 to 10.5. Heat aging is preferably carried out at 80 to 100° C. for 1 to 20 hours, preferably 2 to 15 hours.
  • the aged product obtained in the aging step is placed in a double-arm kneader with a steam jacket and heated and kneaded to obtain an inorganic oxide precursor.
  • the inorganic fibers include glass fibers, silica fibers, alumina fibers, alumina silica fibers, rock wool, and carbon fibers.
  • the average diameter of the inorganic fibers is preferably 0.1-20 ⁇ m, more preferably 5-10 ⁇ m.
  • the average diameter is at least the above lower limit, crevasses can be formed on the surface of the catalyst carrier, and when the average diameter is at most the above upper limit, extrusion molding can be easily performed.
  • the average length of the inorganic fibers is preferably 0.1 mm or more, more preferably 0.5 or more, and the upper limit may be 5 mm, for example.
  • the inorganic fibers can be oriented substantially in the extrusion direction during extrusion molding.
  • These average diameter and average length can be determined, for example, by measuring the diameter and length of 100 randomly selected inorganic fibers on the SEM image and calculating the arithmetic mean value.
  • the inorganic fiber is used in an amount such that the amount in the obtained inorganic oxide carrier is, for example, 0.2 to 10% by mass, preferably 0.5 to 5% by mass.
  • the amount of the inorganic fibers is at least the above lower limit, crevasses can be formed on the surface of the catalyst carrier, and when the amount of the inorganic fibers is at most the above upper limit, extrusion molding can be easily carried out, and strength is increased. A high catalyst can be obtained.
  • step (1) the inorganic oxide or the inorganic oxide precursor (preferably the inorganic oxide precursor) and the inorganic fiber are mixed to obtain a carrier raw material mixture.
  • a conventionally known device such as a steam-jacketed dual-arm kneader can be used.
  • Step (2) is a step of obtaining a molded product by extrusion molding from the carrier raw material mixture obtained in step (1).
  • Extrusion molding can be carried out by a conventionally known method, except that the carrier raw material mixture obtained in step (1) is used as a raw material.
  • Preferred conditions for extrusion molding are as follows.
  • the shape of the molded body includes shapes commonly used in hydrotreating catalysts, such as cylindrical, three-lobed and four-lobed shapes.
  • the size of the shaped body may be, for example, the typical size of shaped bodies used in the production of hydrotreating catalysts. Taking a cylindrical molding as an example, its diameter is, for example, 1 mm to 10 mm, and its length is, for example, 2 to 50 mm.
  • Step (3) is a step of drying and firing the molding obtained in step (2) to obtain an inorganic oxide carrier.
  • This drying and firing is usually performed at 50-800°C. More specifically, the molding is dried by heat-treating it in an air atmosphere at, for example, 50 to 200° C., preferably 75 to 150° C., for example, for 0.5 to 24 hours, preferably 6 to 18 hours. Then, it is calcined by heat treatment at, for example, 350 to 800° C., preferably 400 to 600° C., for 0.5 to 10 hours, preferably 2 to 5 hours, to obtain an inorganic oxide support.
  • Step (4) an impregnation solution containing a raw material for the first metal component, a raw material for the second metal component, and a solvent is prepared, and the impregnation solution is combined with the inorganic oxide support obtained in the step (3).
  • This is a step of contacting to obtain a carrier.
  • first metal component and the second metal component are as described above.
  • Preferred raw materials for the first metal component include, for example, molybdenum trioxide, ammonium molybdate, ammonium metatungstate, ammonium paratungstate, and tungsten trioxide.
  • Preferred materials for the second metal component include, for example, nickel nitrate, nickel carbonate, cobalt nitrate, and cobalt carbonate.
  • the solvent is usually water.
  • the impregnation liquid may further contain a phosphorus component.
  • Preferred examples of the phosphorus component include orthophosphoric acid (hereinafter also simply referred to as “phosphoric acid”), ammonium dihydrogen phosphate, diammonium hydrogen phosphate, trimetaphosphoric acid, pyrophosphoric acid, and tripolyphosphoric acid.
  • the concentration of phosphorus in the impregnating solution is preferably 0.5 to 5.0% by mass in terms of oxide (P 2 O 5 ).
  • the impregnation liquid may further contain an organic acid.
  • Organic acids include, for example, citric acid, malic acid, tartaric acid, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA).
  • Organic additives may be used in addition to organic acids, and examples of organic additives include saccharides (monosaccharides, disaccharides, polysaccharides, etc.). Specifically, for example, glucose (glucose; C 6 H 12 O 6 ), fructose (fructose; C 6 H 12 O 6 ), maltose (maltose; C 12 H 22 O 11 ), lactose (lactose; C 12 H 22 O 11 ), sucrose (sucrose; C 12 H 22 O 11 ), etc. may be added.
  • saccharides monosaccharides, disaccharides, polysaccharides, etc.
  • the impregnating liquid can be prepared by mixing the above components by a conventional method.
  • the prepared impregnating solution is brought into contact with an inorganic oxide carrier to impregnate the inorganic oxide carrier to obtain an inorganic oxide carrier impregnated with the impregnating solution (hereinafter also referred to as "support"). .
  • Step (5) is a step of heat-treating the support obtained in step (4) to obtain a hydrotreating catalyst.
  • This heat treatment is usually performed at 50-800°C. More specifically, the support is heat-treated in an air atmosphere at, for example, 50 to 200° C., preferably 75 to 150° C., for example, for 0.5 to 24 hours, preferably 0.5 to 4.0 hours. and then calcined by heat treatment at, for example, 350 to 800° C., preferably 400 to 600° C., for example, for 0.5 to 5.0 hours, preferably 0.5 to 2.0 hours, to perform inorganic oxidation.
  • the hydrotreating catalyst of the present invention is obtained in which an active metal component is supported on a metal carrier.
  • Examples of light oil include naphtha, kerosene, light gas oil (LGO), heavy gas oil (HGO), vacuum gas oil (VGO), etc.
  • Examples of heavy oil Examples include atmospheric residue (AR), vacuum residue (VR) and the like.
  • ⁇ Method for measuring the content of silica in the catalyst 3 g of a sample obtained by calcining the catalyst at 500 ° C. for 1 hour and then allowing it to cool in a desiccator was collected in a zirconia ball with a lid of 30 ml, heat-treated (200 ° C., 20 minutes), and calcined (700 ° C., 5 minutes), 2 g of Na 2 O 2 and 1 g of NaOH were added and melted for 15 minutes. Further, 25 ml of H 2 SO 4 and 200 ml of water were added and dissolved, and then diluted to 500 ml with pure water to obtain a sample. The obtained sample was measured for silicon content in terms of oxide (SiO 2 ) using an ICP apparatus (ICPS-8100, analysis software ICPS-8000, manufactured by Shimadzu Corporation).
  • step (a) 9.09 kg of an aqueous sodium aluminate solution having a 22% by mass Al 2 O 3 concentration conversion was put into a 100 L (liter) tank with a steam jacket and diluted with deionized water to make 40.00 kg. Next, 230.8 g of an aqueous sodium gluconate solution having a concentration of 26% by mass was added to this solution, and the mixture was heated to 60° C. with stirring to obtain a sodium aluminate/sodium gluconate mixed solution having a concentration of 5% by mass.
  • step (b) Next, the aged alumina hydrate slurry was dehydrated and then washed with 1.5 L of an ammonia aqueous solution having a concentration of 0.3% by mass.
  • step (c) The cake-like slurry after washing is diluted with ion-exchanged water so that the concentration becomes 10% by mass in terms of Al 2 O 3 to form a slurry, and then ammonia water having a concentration of 15% by mass is added to pH 10.2. and aged at 95° C. for 10 hours while stirring.
  • step (d) After aging, the slurry was dewatered, heated while being kneaded by a double-arm kneader with a steam jacket, and concentrated until the alumina concentration reached 20% or more. 0.30 kg of a 10% by mass solution of malic acid was added to the obtained concentrate, and then the mixture was further heated and concentrated and kneaded to a predetermined moisture content.
  • step (e) After that, the resulting kneaded product was molded into a cylindrical shape with a diameter of 1.6 mm using a screw extruder.
  • step (f) Next, after drying the molding at 110° C. for 12 hours, it was calcined at 500° C. for 3 hours to obtain a carrier A. After drying in step (f), crevasses corresponding to the requirements (2) and (3) were not observed on the molding surface.
  • Steps (a) to (d) of the preparation of carrier A were performed.
  • 60 g of glass fiber chopped strands, product name: CS 3DE-704S, manufactured by Nitto Boseki Co., Ltd.
  • carrier B was obtained in the same procedure as the step (f) of preparation of carrier A. After drying in step (f), numerous crevasses corresponding to the requirements (2) and (3) were confirmed on the surface of the molding in a direction substantially perpendicular to the direction of extrusion.
  • step (a) 7.23 kg of sodium aluminate aqueous solution with 22% by mass in terms of Al 2 O 3 concentration is put into a 100 L (liter) tank with a steam jacket, diluted with 39.8 kg of deionized water, and then P 2 O 5 concentration 4.5 kg of sodium phosphate solution of 2.5% by mass in conversion was added with stirring, and the mixture was heated to 60° C. with stirring to prepare a basic aluminum salt mixed aqueous solution.
  • step (b) Next, the aged alumina hydrate slurry was dehydrated and then washed with 120 L of an ammonia aqueous solution having a concentration of 0.3% by mass.
  • step (c) The washed cake-like slurry was diluted with ion-exchanged water to a concentration of 10% by mass in terms of Al 2 O 3 and slurried. After that, aqueous ammonia having a concentration of 15% by mass was added to adjust the pH to 10.3, and the mixture was aged at 95° C. for 10 hours while stirring.
  • step (d) After aging, the slurry was dewatered, heated while being kneaded by a double-arm kneader with a steam jacket, and concentrated and kneaded to a predetermined moisture content.
  • step (e) After that, the resulting kneaded product was molded into a cylindrical shape with a diameter of 1.6 mm using a screw extruder.
  • step (f) Next, after drying the molding at 110° C. for 12 hours, it was calcined at 500° C. for 3 hours to obtain a carrier C. After drying in step (f), crevasses corresponding to requirements (2) and (3) were not observed on the molding surface.
  • Steps (a)-(d) of the preparation of support C were performed.
  • 60 g of glass fiber chopped strands, product name: CS 3DE-704S, manufactured by Nitto Boseki Co., Ltd.
  • carrier D was obtained in the same procedure as the step (f) of preparation of carrier C.
  • step (f) numerous crevasses corresponding to the requirements (2) and (3) were confirmed on the surface of the molding in a direction substantially perpendicular to the direction of extrusion.
  • Steps (a)-(d) of the preparation of support C were performed.
  • 30 g of quartz wool (coarse grade, manufactured by Tosoh Corporation) was added to the kneaded product obtained in step (d), and the kneaded product was further kneaded for 5 minutes. It was molded into a cylindrical shape.
  • Carrier E was then obtained in the same manner as in step (f) of the preparation of carrier C. After drying in step (f), numerous crevasses corresponding to the requirements (2) and (3) were confirmed on the surface of the molding in a direction substantially perpendicular to the direction of extrusion.
  • Example 1 Preparation of hydrotreating catalyst (Al carrier GF)> 780 ml of the impregnating solution a was spray impregnated into 1000 g of the carrier B, dried at 100 ° C. for 1 hour, and calcined at 500 ° C. for 1 hour to obtain a hydrotreating catalyst (hereinafter simply referred to as "catalyst". The same applies to Examples.) was obtained.
  • Example 2 Preparation of hydrotreating catalyst (Al/P carrier GF)> 1000 g of carrier D was impregnated with 780 ml of impregnating liquid a by spraying, dried at 100° C. for 1 hour, and calcined at 500° C. for 1 hour to obtain a hydrotreating catalyst.
  • Example 3 Preparation of hydrotreating catalyst (Al/P-supported SiFiber)> 1000 g of carrier E was impregnated with 780 ml of impregnating solution a by spraying, dried at 100° C. for 1 hour, and calcined at 500° C. for 1 hour to obtain a hydrotreating catalyst.
  • Example 4 Preparation of hydrotreating catalyst (Al carrier GF)> After impregnating 1000 g of the carrier B with 760 ml of the impregnating liquid b by spraying, drying at 100° C. for 1 hour and calcining at 500° C. for 1 hour, a hydrotreating catalyst was obtained.
  • Example 5 Preparation of hydrotreating catalyst (Al/P carrier GF)> 1000 g of carrier D was impregnated with 760 ml of impregnation solution b by spraying, dried at 100° C. for 1 hour, and calcined at 500° C. for 1 hour to obtain a hydrotreating catalyst.
  • Example 7 Preparation of hydrotreating catalyst (Al carrier GF)> After impregnating 1000 g of the carrier B with 770 ml of the impregnating liquid c by spraying, the resultant was dried at 100° C. for 1 hour and then calcined at 500° C. for 1 hour to obtain a hydrotreating catalyst.
  • Example 8 Preparation of hydrotreating catalyst (Al/P carrier GF)> 1000 g of carrier D was impregnated with 770 ml of impregnating solution c by spraying, dried at 100° C. for 1 hour, and calcined at 500° C. for 1 hour to obtain a hydrotreating catalyst.
  • Example 9 Preparation of hydrotreating catalyst (Al/P-supported SiFiber)> 1000 g of carrier E was impregnated with 770 ml of impregnating solution c by spraying, dried at 100° C. for 1 hour, and calcined at 500° C. for 1 hour to obtain a hydrotreating catalyst.
  • VGO vacuum gas oil
  • the Si trapping ability was evaluated using the following method. (1) After confirmation test for evaluation of catalyst performance, it was operated at 360°C for one year. After the operation was stopped, the catalyst was removed, the catalyst was dried in an oven at 110° C. overnight and washed with toluene in a Soxhlet extractor. The washed catalyst was dried overnight in a drier at 110° C. and calcined at 500° C. for 1 hour. The SiO 2 concentrations of the calcined catalysts were measured and compared.
  • a pre-sulfidation treatment was performed on the filled catalyst in order to desorb and activate the oxygen atoms contained in the catalyst.
  • This treatment was carried out by a conventional method, ie, by passing a liquid or gas containing a sulfur compound through a controlled reaction vessel at a temperature of 200 to 400° C. and under a hydrogen pressure atmosphere of normal pressure to 100 MPa.
  • Heavy oil (dense specific gravity at 15 ° C.: 0.9750, sulfur content: 4.06 mass%, metal (Ni + V) content: 85.1 mass ppm, nitrogen content: 2075 mass ppm , asphaltene content: 4.2% by mass, residual carbon content: 10.7% by mass) were introduced and hydrogenated.
  • the reaction conditions at that time were a hydrogen partial pressure of 13.5 MPa, a liquid hourly space velocity of 0.3 h -1 , a hydrogen oil ratio of 800 Nm 3 /kl, and a reaction temperature of 370°C.
  • the metal content in the produced oil obtained was analyzed, and the demetalization rate was determined by the following equation.
  • Demetalization rate (metal concentration in feedstock - metal concentration in hydrotreated oil/metal concentration in feedstock) x 100
  • Tables 2, 3 and 4 show the results of the confirmation tests described above.
  • Example 4 and Comparative Example 3 use the same raw materials except for the presence or absence of inorganic fibers, and can serve as comparison targets for verifying the effects of the present invention.
  • the calculated deposited SiO 2 was defined as the amount of SiO 2 in the spent minus the amount of catalytic SiO 2 before evaluation.
  • the deposited SiO 2 was 6.96% in Example 4 and 4.44% in Comparative Example 3, showing an improvement of 141% in silicon trapping ability.
  • Examples 5 and 6 and Comparative Example 4 use the same raw materials except for the presence or absence of inorganic fibers.
  • the deposited SiO 2 is 6.57% for Example 5, 5.85% for Example 6 and 4.61% for Comparative Example 4.
  • the silicon trapping ability of Example 5 was improved by 141% compared to Comparative Example 4, and the silicon trapping ability of Example 6 was improved by 127% compared to Comparative Example 4, confirming the effects of the invention.
  • a comparison between Example 1 and Comparative Example 1, and a comparison between Examples 2 and 3 and Comparative Example 2 also showed an improvement in the silicon trapping ability.
  • the hydrotreating catalyst of the present invention is industrially extremely useful because it can highly hydrotreat hydrocarbon oils.

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Abstract

Le problème à résoudre par la présente invention est de fournir un catalyseur d'hydrotraitement pour des huiles hydrocarbonées qui a une activité d'hydrodésulfuration, une capacité d'hydrodémétallisation et une capacité de piégeage de silicium améliorées. La solution selon l'invention porte sur un catalyseur d'hydrotraitement pour des huiles hydrocarbonées qui comprend un support d'oxyde inorganique et un composant métallique actif supporté sur le support d'oxyde inorganique. Le composant métallique actif comprend un premier métal qui est le molybdène et/ou le tungstène, et un second métal qui est le cobalt et/ou le nickel. Les exigences (1) à (3) suivantes sont satisfaites dans la distribution de volume des pores différentiel logarithmique mesurée par la technique d'intrusion de mercure. Exigence (1) : dV/d(logD) est à un maximum absolu dans la plage de diamètre des pores de 5 à 30 nm. L'exigence (2) : dV/d(logD) est à un maximum local dans la plage de diamètre des pores de 2 à 50 µm. Exigence (3) : le rapport du volume des pores dans la plage de diamètre des pores de 2 à 50 µm au volume total des pores est égal ou supérieur à 3 %.
PCT/JP2022/006712 2021-03-31 2022-02-18 Catalyseur d'hydrotraitement pour huile hydrocarbonée et son procédé de production WO2022209410A1 (fr)

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Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60193539A (ja) * 1984-03-15 1985-10-02 Chiyoda Chem Eng & Constr Co Ltd 繊維性粘土鉱物を含有する組成物の製造方法
JPH0427436A (ja) * 1990-05-22 1992-01-30 Catalysts & Chem Ind Co Ltd 水素化処理触媒およびその製造方法
JP2006181562A (ja) * 2004-12-24 2006-07-13 Catalysts & Chem Ind Co Ltd 重質炭化水素油の水素化処理触媒組成物およびその製造方法
WO2016189982A1 (fr) * 2015-05-27 2016-12-01 日揮触媒化成株式会社 Catalyseur d'hydrotraitement pour huile hydrocarbonée, procédé de production correspondant, et procédé d'hydrotraitement
CN109718857A (zh) * 2017-10-27 2019-05-07 中国石油化工股份有限公司 加氢精制催化剂及其制备方法和应用以及馏分油的加氢精制方法

Patent Citations (5)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JPS60193539A (ja) * 1984-03-15 1985-10-02 Chiyoda Chem Eng & Constr Co Ltd 繊維性粘土鉱物を含有する組成物の製造方法
JPH0427436A (ja) * 1990-05-22 1992-01-30 Catalysts & Chem Ind Co Ltd 水素化処理触媒およびその製造方法
JP2006181562A (ja) * 2004-12-24 2006-07-13 Catalysts & Chem Ind Co Ltd 重質炭化水素油の水素化処理触媒組成物およびその製造方法
WO2016189982A1 (fr) * 2015-05-27 2016-12-01 日揮触媒化成株式会社 Catalyseur d'hydrotraitement pour huile hydrocarbonée, procédé de production correspondant, et procédé d'hydrotraitement
CN109718857A (zh) * 2017-10-27 2019-05-07 中国石油化工股份有限公司 加氢精制催化剂及其制备方法和应用以及馏分油的加氢精制方法

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