WO2017135193A1 - 炭化水素油の水素化処理触媒、その製造方法、および水素化処理方法 - Google Patents

炭化水素油の水素化処理触媒、その製造方法、および水素化処理方法 Download PDF

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WO2017135193A1
WO2017135193A1 PCT/JP2017/003197 JP2017003197W WO2017135193A1 WO 2017135193 A1 WO2017135193 A1 WO 2017135193A1 JP 2017003197 W JP2017003197 W JP 2017003197W WO 2017135193 A1 WO2017135193 A1 WO 2017135193A1
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carrier
mass
alumina
catalyst
parts
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PCT/JP2017/003197
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English (en)
French (fr)
Japanese (ja)
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雄介 松元
渡部　光徳
みどり 小林
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日揮触媒化成株式会社
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Priority claimed from JP2016087499A external-priority patent/JP6681259B2/ja
Application filed by 日揮触媒化成株式会社 filed Critical 日揮触媒化成株式会社
Priority to CN201780009213.2A priority Critical patent/CN108602055A/zh
Priority to SG11201806008PA priority patent/SG11201806008PA/en
Priority to KR1020187021436A priority patent/KR102608017B1/ko
Publication of WO2017135193A1 publication Critical patent/WO2017135193A1/ja

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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
    • B01J27/02—Sulfur, selenium or tellurium; Compounds thereof
    • B01J27/04—Sulfides
    • B01J27/047—Sulfides with chromium, molybdenum, tungsten or polonium
    • B01J27/051—Molybdenum
    • B01J27/0515—Molybdenum with iron group metals or platinum group metals
    • 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
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/88—Molybdenum
    • B01J23/883—Molybdenum and nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/85—Chromium, molybdenum or tungsten
    • B01J23/888—Tungsten
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • 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
    • 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
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • 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
    • B01J35/64—Pore diameter
    • B01J35/647—2-50 nm
    • 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
    • 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
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/0201—Impregnation
    • 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
    • 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
    • B01J37/20—Sulfiding
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G45/00—Compounds of manganese
    • C01G45/08—Nitrates
    • 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 content in hydrocarbon oil in the presence of hydrogen, a production method thereof, and a hydrotreating method.
  • a catalyst is used to advance the reaction under high temperature and high pressure.
  • the activity of the catalyst is high because the economics of the process are enhanced by reducing the reaction conditions at low temperature and low pressure.
  • Patent Document 1 a sulfide catalyst containing a base metal element selected from Groups 8 to 10 of the periodic table such as nickel, cobalt, molybdenum, tungsten, etc. is added to Groups 8 to 10 of the Periodic Table of rhodium, palladium, platinum, and the like. It has been reported that by adding selected noble metals, high hydrotreating performance is exhibited by utilizing spillover hydrogen. In addition, it is described that it is desirable that the behavior of the catalyst component that serves as a reaction active point undergoes reduction is closely related to the catalytic activity of the hydrotreatment, and the reduction peak temperature of the catalyst under a hydrogen stream is 500 ° C. or less. Has been.
  • Patent Document 2 discloses a method for producing an alumina carrier prepared from a boehmite sol using a pH adjuster as a method for producing a heat-resistant alumina carrier for catalytic combustion, and even when used in a high temperature atmosphere of 1000 ° C. or higher. The effect that a high surface area can be stably maintained is described. This finding is expected that the boehmite used is sol-like and thin, pH adjustment is somewhat complicated, and is somewhat unsuitable industrially.
  • Patent Document 3 discloses a method for producing an alumina catalyst carrier using an alumina hydrate having a pseudoboehmite crystal structure.
  • water is added to the hydrated alumina to plasticize it, and the plasticized product is kneaded and adjusted to an arbitrary pseudoboehmite crystal size, whereby an alumina support having a desired pore size can be obtained. It is described that it can be manufactured.
  • the crystal size is controlled by the reaction temperature and reaction time of the plasticized product, and many skills are required for property management, and in many cases the quality is expected to be unstable.
  • Patent Document 4 discloses a method for producing an alumina carrier using pseudo boehmite alumina powder, and this production method is a method for producing a highly pure and highly active alumina catalyst carrier by adjusting the particle shape of an alumina raw material. It is grasped that there is.
  • this manufacturing method a method of changing the aspect ratio of the particles by changing the mixing ratio of the two kinds of alumina raw material powders is taken, and the adjustment is expected to largely depend on the alumina raw material and its mixed state. Is done.
  • Patent Document 5 a catalyst obtained by supporting an active metal such as cobalt, nickel, molybdenum and tungsten on a ⁇ -alumina carrier and calcining is further impregnated with polyethylene glycol as an organic additive, and the organic additive remains in the catalyst.
  • a method for producing a hydrogenation catalyst characterized by drying under such conditions has been reported.
  • the effect of promoting the hydrodesulfurization reaction by allowing the organic additive to remain can be expected.
  • the carbonaceous material derived from organic additives is very unstable and not only affects the stability of the performance during use, but also the performance recovery rate of the used catalyst regenerated product is very poor. Need to supplement the burned-out organic additives.
  • Patent Document 6 as a method for producing porous alumina, water and at least one monobasic acid or salt thereof are added to one or more kinds of aluminum hydroxide and / or alumina, and a sol-formation reaction is performed in a temperature range of 250 ° C. or less.
  • a production method characterized in that an aqueous alumina gel and / or alumina gel is obtained by performing, and the aqueous alumina gel and / or alumina gel is dried and fired.
  • Patent Document 5 describes a method of adding an oxygen-containing organic substance, an inorganic polybasic acid, or the like as a pore control agent to an alumina preparation solution.
  • the additive is used only in one step, and the catalyst performance is greatly increased.
  • Patent Document 7 describes a process for aging alumina hydrate fine particles to which a buffer material and a peptizer are added as a method for producing alumina hydrate fine particle powder, but the crystallinity of alumina is touched. Not.
  • Patent Document 8 includes a process for forming molded particles containing at least 90% by weight of boehmite as a method for producing a highly active hydrodesulfurization catalyst, and converting it into ⁇ -alumina by heat treatment. It is described that the amount is ⁇ -alumina (alumina other than ⁇ -alumina is less than 10% by weight). However, the crystallinity control factor is only the firing temperature.
  • Patent Document 9 discloses a method for producing a catalyst using a phosphorus-silica-alumina support as the inorganic composite oxide support. Phosphorus-containing alumina hydrate is obtained by mixing an aluminum salt solution containing phosphate ions and a neutralizing agent so that the pH is 6.5 to 9.5, and the hydrate is washed.
  • Patent Document 10 describes a particulate support made of an oxide selected from alumina, silica, titania, zirconia, and zeolite and having a diameter of 2 to 7 mm, and a catalyst using this support. In addition to the fact that a cross-section of this granular material is observed at a magnification of 10,000 times with a transmission electron microscope and a shell-like concentrated layer is observed, it is a granular hydroprocessing catalyst support and an average pore diameter. Is different from this case in that it is characterized by the relatively large 150-300 mm.
  • Patent Document 11 discloses a catalyst of a fixed bed reactor containing an alumina-based support composed of a plurality of juxtaposed agglomerates and a total of 0.1 to 50% by weight of active metals.
  • An inorganic composite oxide support containing at least one additive element from the group consisting of phosphorus, boron, silicon, and halogens is used, but a part of the stack of thin plates and the aggregate in the form of needles
  • the needle-shaped object is characterized in that it is uniformly and uniformly distributed around the stack of thin plate-like objects and between the thin plate-like objects. The point that it is a carrier made of aggregates is very different from this case.
  • Patent Document 12 discloses a method for producing a catalyst carrier containing a considerable amount of at least one metal oxide of Group IVB of the Periodic Table of Elements and containing silica, and uses thereof.
  • the mass ratio of the amount of the group IVB metal oxide and the amount of silica contained in the carrier is between 5 and 70, and the carrier is characterized by mixing silica and titanium or zirconium.
  • the carrier composition is different from this case.
  • Patent Document 13 discloses a support containing titanium, a method for producing the same, a hydrotreating catalyst for hydrocarbon oil, and a hydrotreating method using the same.
  • the carrier contains a refractory inorganic oxide and / or activated carbon containing a basic oxide that is an oxide of titanium and a rare earth metal, and titanium is uniformly supported on the refractory inorganic oxide and / or activated carbon. It is a feature. However, it is a production method in which a titanium-containing aqueous solution is brought into contact with a refractory inorganic oxide carrier by an impregnation method, and it is expected to be complicated and somewhat unsuitable industrially because of many processes.
  • Patent Document 14 and Patent Document 15 describe a method for producing a high-performance hydrotreating catalyst using an inorganic composite oxide support in which alumina is mixed with phosphorus, phosphorus and titania.
  • these are major features in that they are unfired catalysts characterized by containing 2% by mass or more of organic acid-derived carbon on a catalyst basis.
  • it is assumed that regeneration of the catalyst is difficult while having high performance.
  • Japanese Patent Laid-Open No. 2002-210362 Japanese Patent Laid-Open No. 07-256100 JP 07-155597 A WO97 / 12670 publication JP-A-8-332385 WO2001 / 056951 Publication JP 2014-133687 A WO2006 / 034073 JP 2000-135437 A JP 11-319554 A JP 2000-176288 A Japanese Patent Laid-Open No. 2001-17860 JP 2004-074148 A JP 2009-101362 A JP 2013-028474 A
  • An object of the present invention is to provide a hydrotreating catalyst for hydrocarbon oil that is excellent in desulfurization activity while maintaining high industrial productivity and can regenerate a high-performance catalyst, and a method for producing the same.
  • Another object of the present invention is to provide a method for hydrotreating hydrocarbon oil that can remove sulfur in hydrocarbon oil at a high removal rate.
  • the hydrocarbon oil hydrotreating catalyst of the present invention is: (1) A carrier mainly composed of alumina, which is a or b below: a. Made of 100% ⁇ -alumina b. 80 to 98 parts by mass of aluminum in terms of alumina is contained with respect to 100 parts by mass of the carrier, and the carrier is obtained from the half width of the XRD diffraction spectrum (020) peak of pseudoboehmite of alumina which is the main component in the precursor.
  • the catalyst has a specific surface area of 200 to 320 m 2 / g, and for the carrier b, the catalyst has a specific surface area of 180 to 320 m 2 / g.
  • the pore diameter is 50 to 110 mm; (5) The ignition loss is 5.0% by mass or less, (6) The carbon derived from the organic acid is 2.0 parts by mass or less as an element basis with respect to 100 parts by mass of the catalyst, (7) the adsorption amount of nitric oxide of the sulfurized catalyst is 8.0 ml / g or more; It is provided with.
  • the carrier is made of 100 parts by mass of ⁇ -alumina, and the crystallite diameter determined from the half width of the XRD diffraction spectrum (020) peak of pseudoboehmite of alumina as a precursor is 45 mm or less.
  • the method of the present invention for producing a hydrocarbon oil hydrotreating catalyst according to the present invention is as follows.
  • the carrier is the carrier described in (1) a above (a carrier comprising 100 parts by mass of ⁇ -alumina), (A) a first aging step of aging a slurry containing alumina obtained by mixing an aqueous solution of an basic aluminum salt and an aqueous solution of an acidic aluminum salt; Cleaning the aged slurry after dehydration, A second aging step of aging the slurry containing the washed object; Then, kneading and concentrating the slurry, Forming a concentrated concentrate of the slurry; A step of drying and firing the molded product, and preparing a ⁇ -alumina carrier; (B) preparing an impregnating solution comprising a first metal component that is at least one of molybdenum and tungsten, a second metal component that is at least one of cobalt and nickel, and an organic acid; Supporting the metal component and the second metal component on the ⁇ -alumina support, (C) The step of obtaining a hydrotreating catalyst by heat-tre
  • a first organic compound is added to the slurry.
  • the first organic compound is added, for example, in the range of 0.5 to 5.0 parts by mass with respect to 100 parts by mass of alumina.
  • the second organic compound is added before the step of forming the concentrate.
  • the second organic compound is added, for example, in the range of 0.5 to 5.0 parts by mass with respect to 100 parts by mass of alumina.
  • the organic compound is, for example, at least one of organic acids and saccharides.
  • the basic aluminum salt aqueous solution in the step (A) contains a carboxylate.
  • the alumina concentration is less than 20%, and in the step of kneading and concentrating the slurry in the step (A), the alumina concentration is 20% or more. It is.
  • the temperature of the heat treatment in the step (A) is 100 to 600 ° C.
  • the technique described above corresponds to the case where the carrier corresponds to the carrier described in (1) a above (a carrier made of 100 parts by mass of ⁇ -alumina).
  • the carrier contains 80 to 98 parts by mass of aluminum in terms of alumina with respect to 100 parts by mass of the carrier, and the carrier is an XRD diffraction spectrum (020) peak of pseudoboehmite of alumina which is the main component in the precursor.
  • the crystallite diameter determined from the half-value width of 15 to 40 mm.
  • the inorganic composite oxide carrier corresponds to the basic OH group with respect to the absorbance Sa of the spectral peak in the wave number range of 3675 to 3678 cm ⁇ 1 corresponding to the acidic OH group measured by a transmission Fourier transform infrared spectrophotometer.
  • the ratio Sb / Sa of absorbance Sb of spectral peaks in the wave number range of 3770 to 3774 cm ⁇ 1 is in the range of 0.20 to 0.45.
  • the inorganic composite oxide carrier has a diffraction peak area P1 indicating the aluminum crystal structure attributed to the boehmite (020) plane and a diffraction peak area indicating the crystal structure of the ⁇ -alumina (440) plane measured from the XRD diffraction spectrum. Assuming P2, the ratio P2 / (P1 + P2) of P2 to the total value of P1 and P2 is 0.9 or more.
  • the method for producing the hydrotreating catalyst for hydrocarbon oil of the present invention (when the carrier corresponds to b in (1) above) (D) a step of preparing an inorganic composite oxide support; (E) a first metal component that is at least one of molybdenum and tungsten; a second metal component that is at least one of cobalt and nickel; and an organic acid And a step of supporting the first metal component and the second metal component on the inorganic composite oxide support, (F) The inorganic composite oxide support carrying the first metal component and the second metal component obtained by the step (E) is heated at a temperature of 100 to 600 ° C. to be hydrotreated. Obtaining a catalyst; It is characterized by including.
  • step of preparing the inorganic composite oxide support of (1) (D-1) a slurry preparation step of preparing a composite metal hydrate slurry by mixing an aqueous solution of a basic metal salt and an aqueous solution of an acidic metal salt; (D-2) a first aging step of aging the composite metal hydrate slurry; (D-3) Next, washing the composite metal hydrate slurry; (D-4) Then, a second aging step of aging the composite metal hydrate slurry, (D-5) Thereafter, a kneading / concentrating step of kneading and concentrating the composite metal hydrate slurry; (D-6) molding the concentrate obtained by concentrating the composite metal hydrate slurry; (D-7) Next, drying and firing the molded body, In the second aging step (D-4), the first organic compound is added.
  • the basic aluminum salt aqueous solution in the slurry preparation step (D-1) contains a carboxylate.
  • the first organic compound is added in the range of 0.5 to 4.0 parts by mass with respect to 100 parts by mass of the inorganic composite oxide.
  • the second organic compound is added in the range of 0.5 to 4.0 parts by mass with respect to 100 parts by mass of the inorganic composite oxide.
  • the concentration of the inorganic composite oxide in the slurry in the second ripening step (D-4) is less than 20%, and the concentration of the inorganic composite oxide in the slurry in the kneading / concentration step (D-5) is 20%. That's it.
  • the organic compound is at least one selected from citric acid, malic acid, tartaric acid, gluconic acid, acetic acid, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), and sugars (monosaccharides, polysaccharides, etc.). .
  • the present invention is not limited to the specific example described in this item.
  • the hydrocarbon oil hydrotreating method of the present invention comprises a hydrogen partial pressure of 3 to 8 MPa, a temperature of 260 to 420 ° C., and a liquid space velocity of 0.3 to 5 hr in the presence of the hydrotreating catalyst of the present invention.
  • -Hydrocarbon oil is hydrotreated under the conditions of -1 .
  • the hydrotreating catalyst of the present invention high strength, high stability, a large surface area can be obtained by using a carrier made of ⁇ -alumina, crystallinity can be easily controlled, and high productivity can be expected.
  • the hydrotreating catalyst of the present invention uses a support made of an inorganic composite oxide mainly composed of ⁇ -alumina and having improved dispersibility of foreign elements, so that a highly active catalyst with a large surface area and high strength can be obtained. You can expect to get. And since it is a suitable active metal composition, the high dispersibility of an active metal is obtained, and the increase in the adsorption amount of nitric oxide (NO) used as the parameter
  • NO nitric oxide
  • the hydrodesulfurization method of hydrocarbon oil with high desulfurization activity can be implemented by using the hydrotreating catalyst for hydrocarbon oil of the present invention.
  • the hydrocarbon oil hydrotreating catalyst (hereinafter also referred to as “the catalyst of the present invention” in the first embodiment) according to the first embodiment of the present invention is a ⁇ -alumina carrier (hereinafter also referred to as an alumina carrier). ) And an active metal component, and has predetermined properties.
  • the ⁇ -alumina support, the active metal component and the catalyst are described in detail below.
  • the ⁇ -alumina support constituting the hydrotreating catalyst is an aluminum oxide excluding impurities, and its crystal state can be classified as ⁇ -alumina, and is 100% ⁇ -alumina.
  • the term “100% ⁇ -alumina” means that impurities contained inevitable from the production process of the alumina carrier can be contained, but not contained otherwise.
  • the content of ⁇ -alumina in the alumina carrier is 99%. It is at least mass% (parts by mass), preferably at least 99.5 mass%.
  • a hydrotreating catalyst not only high performance but also high industrial productivity can be maintained.
  • a porous support is usually used and has a relatively small pore having a pore diameter of 500 mm or less. Are preferably used.
  • an appropriate binder component or additive can be contained in the formation of the support or catalyst body.
  • the catalyst support of the present invention corresponds to a basic OH group with respect to absorbance Sa of a spectral peak in the wave number range of 3673 to 3678 cm ⁇ 1 corresponding to an acidic OH group measured by a transmission Fourier transform infrared spectrophotometer.
  • the ratio Sb / Sa of the absorbance Sb of the spectral peak in the wave number range of 3770 to 3774 cm ⁇ 1 is in the range of 0.15 to 0.40.
  • the ratio Sb / Sa is more preferably in the range of 0.20 to 0.40.
  • the active metal is known to have different dispersibility depending on the characteristics of the alumina support surface. When Sb / Sa is in the above range, the high dispersibility of the active metal on the support surface is particularly noticeable.
  • FIG. 1 shows a support of the catalyst of the present invention (supports A and K shown in Examples) having a wave number range of 3673 to 3678 cm ⁇ 1 corresponding to acidic OH groups and 3770 to 3774 cm ⁇ 1 corresponding to basic OH groups.
  • An example of a light absorption spectrum including a wave number range will be shown.
  • a calcination process is performed to prepare ⁇ -alumina via the pseudoboehmite crystal state, but the precursor of pseudoboehmite of alumina (before calcination) is used.
  • the crystallite diameter determined from the half width of the XRD diffraction spectrum (020) peak is characterized by being 45 mm or less. Control of the crystallite size of pseudoboehmite is important because it affects the difficulty of crystal transition by subsequent firing as well as optimization of the pore structure of the alumina support. When the crystallite size exceeds 45 mm, the average pore diameter is large and the specific surface area is small, which is not preferable because the performance of the catalyst may be lowered. In addition, since it is difficult for the crystal transition to proceed during calcination, a boehmite structure may remain in the crystal form of the alumina support, which may cause a concern that the stability of the catalyst performance may be impaired.
  • the first metal component may be tungsten instead of molybdenum, or both molybdenum and tungsten.
  • a preferable range of the content (supported amount) of the first metal component is 15 to 27% by mass in terms of oxide on the catalyst basis (15 to 27 parts by mass in terms of oxide with respect to 100 parts by mass of catalyst). A more preferable range is 15 to 20% by mass.
  • the second metal component may be nickel instead of cobalt, or both cobalt and nickel.
  • the content (supported amount) of the second metal component must be 2 to 7% by mass in terms of oxide on the catalyst basis (2 to 7 parts by mass in terms of oxide with respect to 100 parts by mass of catalyst). It is.
  • the second metal component acts as a promoter for the first metal component, and when the content is less than 2% by mass in terms of oxide, the first metal component and the second metal component which are active metal components However, when it becomes difficult to maintain an appropriate structure and the content exceeds 7% by mass in terms of oxide, aggregation of the active metal component tends to proceed and the catalyst performance decreases.
  • an organic acid is usually contained in the impregnation liquid, and thus the organic acid becomes a carbon supply source supported on the alumina support.
  • the organic acid used for the active metal component include citric acid, malic acid, gluconic acid, tartaric acid, ethylenediaminetetraacetic acid (EDTA), and diethylenetriaminepentaacetic acid (DTPA), and more preferably citric acid and malic acid. , Tartaric acid, gluconic acid and the like.
  • organic acids for example, when using organic additives such as saccharides (monosaccharides, disaccharides, polysaccharides, etc.), in this specification, the content of carbon derived from organic acids refers to organic acids. And the content of carbon derived from both organic additives.
  • the catalyst of the present invention needs to have a specific surface area (SA) measured by the BET (Brunauer-Emmett-Teller) method in the range of 200 to 320 m 2 / g.
  • SA specific surface area measured by the BET (Brunauer-Emmett-Teller) method
  • the specific surface area (SA) is smaller than 200 m 2 / g, the metal components are likely to aggregate and the desulfurization performance may be deteriorated.
  • SA specific surface area measured by the BET (Brunauer-Emmett-Teller) method
  • SA Brunauer-Emmett-Teller
  • the average pore diameter is a value measured by a mercury intrusion method (mercury contact angle: 130 degrees, surface tension: 480 dyn / cm), and represents a pore diameter corresponding to 50% of the total pore volume.
  • the pore volume represents the volume of pores having a pore diameter of 41 mm or more. If the average pore size is less than 50%, the desulfurization performance may be reduced, and if the average pore size is greater than 110%, the catalyst strength may be reduced.
  • the catalyst of the present invention has an ignition loss (Ig Loss) of 5.0% by mass or less.
  • the ignition loss can be obtained by heating the catalyst at a high temperature as described in the item of the measurement method described later.
  • the ⁇ -alumina carrier is impregnated with the impregnation liquid and then calcined at a temperature of, for example, 300 ° C. or more.
  • the loss on ignition of the catalyst is assumed to be 80% or more. Can do.
  • the ignition loss of the catalyst increases. There is a concern that the active metal component agglomerates during the calcination step during catalyst regeneration.
  • the desulfurization performance of an unused catalyst (fresh catalyst) with a novel activity during catalyst regeneration is 100%. 80% or more. If the carbon content is large, there is a concern that the active metal component aggregates due to the firing step during catalyst regeneration.
  • the catalyst of the present invention has a peak temperature of desorbed water in the range of up to 450 ° C. (temperature at which the peak of the desorption spectrum of water appears) based on the catalyst temperature reduction method is 415 ° C. or lower. A specific example of the temperature reduction method will be described later.
  • the sulfidation treatment is performed on molybdenum with hydrogen sulfide or the like under a hydrogen stream, and the reaction requires oxygen to be desorbed from molybdenum oxide. Since the desorption peak of water is just the detection of desorption of oxygen from the molybdenum oxide as water, the progress of the sulfidation treatment and the reduction temperature of molybdenum are considered to have a correlation. Therefore, it is considered that the sulfurization treatment of molybdenum can be sufficiently advanced by lowering the peak temperature of the desorbed water.
  • the reduction temperature is too high, that is, if the peak temperature of the desorbed water is too high, the water is weakly interacting with the alumina support, so there is a high possibility that active metal aggregates are present. . For this reason, it is presumed that the sulfurization process does not proceed sufficiently. Therefore, it is necessary to lower the reduction temperature and to reduce the interaction between water and the alumina support in order to highly disperse the active metal.
  • the desorbed water is mainly produced in the molybdenum reduction process, and its peak temperature varies depending on the carrier composition, active metal composition and the like. According to the knowledge of the present inventor, in order to set the desorption peak temperature of water (peak temperature of desorption water) to 415 ° C.
  • the alumina support at least one of molybdenum and tungsten (as the active metal component) ( It is necessary that at least one of cobalt and nickel (1 type) is 2 to 7% by mass in terms of oxide.
  • the amount of the active metal component is less than this range, the catalyst performance is insufficient, which is not preferable.
  • the amount of the active metal component is more than this range, it is not preferable because an aggregate of the active metal is generated and the dispersibility may be impaired. .
  • the adsorption amount of nitric oxide of the sulfurized catalyst is 8.0 ml / g or more.
  • the adsorption amount is more preferably 8.3 ml / g or more.
  • the reaction active point of the catalyst can be measured.
  • the reaction activity point of the catalyst is small and the effect of improving the catalyst performance cannot be obtained.
  • the amount of nitrogen monoxide adsorbed after sulfiding the catalyst varies depending on the physical and chemical characteristics of the support, the active metal composition, and the like.
  • the specific surface area (SA) of the alumina support is in the range of 180 to 320 m 2 / g, b) to the absorbance Sa spectral peaks in the wave number range of transmission Fourier transform infrared corresponding to acidic OH groups measured by the outside spectrophotometer 3674 ⁇ 3678cm -1, corresponding to the basic OH groups 3770 ⁇ 3774cm -1
  • an active metal component on the alumina support at least one of molybdenum and tungsten is 15 to 28%
  • the method for producing a hydrocarbon oil hydrotreating catalyst according to the present invention comprises: a first step of preparing a ⁇ -alumina support; An impregnating solution comprising a first metal component that is at least one of molybdenum and tungsten, a second metal component that is at least one of cobalt and nickel, and an organic acid is prepared, and the first metal component And a second step of supporting the second metal component on the alumina support, A third step of obtaining a hydrotreating catalyst by heat-treating the alumina support carrying the first metal component and the second metal component obtained at the second step at a temperature of 100 to 600 ° C .; Have.
  • each step will be described.
  • Step of obtaining alumina slurry First, a basic aluminum salt aqueous solution and an acidic aluminum salt aqueous solution are mixed so that the pH is 6.5 to 9.5, preferably 6.5 to 8.5, and more preferably 6.8 to 8.0. Thus, a hydrate of inorganic oxide is obtained. At this time, the basic aluminum salt aqueous solution preferably contains a carboxylate. Then, after aging the slurry of inorganic oxide hydrate by a desired method (first aging step), washing is performed to remove the by-product salt, and a slurry containing alumina is obtained.
  • the carboxylates used here are polyacrylic acid, hydroxypropyl cellulose, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid, gluconic acid, fumaric acid, phthalic acid, citric acid, etc.
  • the salt is preferably added in the range of 0.5 to 5.0 parts by mass with respect to 100 parts by mass of alumina. ⁇ 1-2.
  • Second aging process for alumina At least one organic compound (first organic compound) is added to the hydrate slurry obtained in the step 1-1, and the temperature is 30 ° C. or higher, preferably 80 to 100 in an aging tank equipped with a reflux.
  • the aging is carried out at a temperature of, for example, 1 to 20 hours, preferably 2 to 10 hours (second aging step).
  • the alumina concentration is preferably less than 20%.
  • Kneading, molding and drying process >> The aged product obtained in the step 1-2 is placed in a double-arm kneader with a steam jacket, heated and concentrated until the alumina concentration becomes 20% or more, and then at least one organic compound (second organic compound). After that, the mixture is further heated and kneaded to obtain a moldable kneaded product, and then molded into a desired shape by extrusion molding or the like.
  • the timing of the addition of the second organic compound may be during the concentration of the aged product.
  • Heat treatment (drying and firing) process >> The molded product obtained in the 1-3 step is then heat-dried at, for example, 70 to 150 ° C., preferably 90 to 130 ° C., more preferably 400 to 800 ° C., preferably 400 to 600 ° C., for example 0 Calcination for 5 to 10 hours, preferably 2 to 5 hours, to obtain an alumina support.
  • As the basic aluminum salt used here sodium aluminate, potassium aluminate and the like are preferably used.
  • As the acidic aluminum salt aluminum sulfate, aluminum chloride, aluminum nitrate, or the like is preferably used.
  • the temperature is usually kept at 40 to 90 ° C., preferably 50 to 70 ° C., and the temperature of this solution is ⁇ 5 ° C., preferably ⁇ 2 ° C., more preferably
  • the mixed aqueous solution heated to ⁇ 1 ° C. is usually 5 to 20 so that the pH is 6.5 to 9.5, preferably 6.5 to 8.5, more preferably 6.5 to 8.0. Minutes, preferably 7-15 minutes, to form a precipitate to obtain a hydrate slurry.
  • the time required for the addition of the mixed aqueous solution to the basic aluminum salt aqueous solution is preferably 15 minutes or less because undesirable crystals such as bayerite and gibbsite may be generated in addition to pseudoboehmite when it is long. 13 minutes or less is more desirable. Bayerite and gibbsite are not preferred because their specific surface area decreases when heat-treated. Moreover, as a 1st organic compound and a 2nd organic compound used at the said 1st process, at least 1 sort (s) chosen from organic acids or saccharides is preferable.
  • the addition amount is desirably in the range of 0.5 to 5.0 parts by mass with respect to 100 parts by mass of alumina. If the addition amount is less than this range, it is difficult to obtain the effect due to the addition of the organic compound, and if it exceeds this range, the pore structure becomes too small due to the effect that is too strong, and the physical properties of the catalyst are not in the optimum range. This is not preferable because the efficiency of the preparation is deteriorated.
  • the OH group on the surface of the carrier is an important factor that affects the loading state, such as the dispersibility of the active metal species.
  • the control of the OH group can be performed at any point in the carrier preparation step together with the crystallinity of the carrier alumina precursor.
  • ⁇ Second step> The impregnating liquid containing the first metal component, the second metal component, and the carbon component described above is brought into contact with the alumina support.
  • the raw material for the first metal component for example, molybdenum trioxide, ammonium molybdate, ammonium metatungstate, ammonium paratungstate, tungsten trioxide and the like are preferably used.
  • a raw material of a 2nd metal component nickel nitrate, nickel carbonate, cobalt nitrate, cobalt carbonate, etc. are used suitably.
  • orthophosphoric acid (hereinafter also simply referred to as “phosphoric acid”), ammonium dihydrogen phosphate, diammonium hydrogen phosphate, trimetaphosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, etc. are used. .
  • the impregnating solution is preferably made to have a pH of 4 or less using an organic acid to dissolve the metal component.
  • pH exceeds 4 it exists in the tendency for the stability of the metal component which melt
  • the organic acid for example, citric acid, malic acid, tartaric acid, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA) can be used, and citric acid and malic acid are particularly preferably used.
  • saccharides monosaccharide, disaccharide, polysaccharide, etc.
  • Organic additives such as 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 ) and the like may be added.
  • the carrier carrying the metal component obtained by contacting with the impregnating liquid in the second step is 100 to 600 ° C., preferably 110 to 600 ° C., more preferably 400 to 600 ° C., for 0.5 to 10 hours, preferably After heat treatment for 1 to 8 hours, the hydrotreating catalyst of the present invention is produced.
  • the firing temperature is excessively lower than 100 ° C., the operability due to residual moisture may be deteriorated, and the metal supporting state may be difficult to be uniform. If it exceeds 600 ° C., the metal causes aggregation and dispersion. Since there is a possibility that the maintenance effect cannot be expected, it is not preferable.
  • one of the advantages in the first to third steps will be described.
  • the organic compound (1st organic compound) is added to the slurry of a hydrate, and it heat-ages.
  • the crystallite diameter of pseudoboehmite of alumina as a precursor can be reduced to 45 mm or less, the average pore diameter of the catalyst can be reduced, and the specific surface area can be increased.
  • the boehmite structure is less likely to remain in the crystal form of the alumina support, and the catalyst performance can be stabilized.
  • a catalyst that satisfies both a high surface area and a high strength in a balanced manner is desired.
  • a calcination step is performed via a pseudo boehmite crystal state, and it has been expected that the performance of the catalyst is improved by controlling the crystal state of the pseudo boehmite.
  • the crystal state of pseudo boehmite can be controlled, which contributes to the production of a high-performance hydroprocessing catalyst.
  • the hydrocarbon oil to be desulfurized by the hydrotreating catalyst of the present invention is, for example, straight-run kerosene or straight-run light oil obtained from a crude oil atmospheric distillation device, straight-run heavy oil obtained from an atmospheric distillation device Hydrogenation of reduced pressure light oil or reduced pressure heavy light oil obtained by treating oil and residual oil with a vacuum distillation apparatus, catalytic cracked kerosene or contact cracked light oil obtained by catalytic cracking of desulfurized heavy oil, reduced pressure heavy light oil or desulfurized heavy oil Examples include hydrocracked kerosene or hydrocracked light oil obtained by cracking, pyrolyzed kerosene or pyrolyzed light oil obtained from a thermal cracking device such as a coker, and a fraction having a boiling point of 180 to 390 ° C. is 80% by volume or more. This is the fraction that contains it.
  • the hydrogenation treatment using the catalyst is carried out under a high-temperature and high
  • ⁇ Alumina crystal state identification and crystallite size measurement method An X-ray diffractometer (manufactured by Rigaku Denki Co., Ltd .: RINT2100) was used, and the measurement sample was a compacted non-reflective plate for measurement as an observation sample, and the crystal state was measured by X-ray diffraction.
  • the crystallite size of the support alumina precursor was calculated by the Scherrer method from the (020) plane attributed to boehmite, and the crystal structure of the baked support was judged by comparing the diffraction peaks attributed to boehmite and ⁇ -alumina. .
  • the alumina oxide support of the present case is preferably ⁇ -alumina, specifically, the diffraction peak areas indicating the crystal structures of the boehmite (020) plane and (120) plane measured by X-ray diffraction analysis, It is necessary to be less than 1/10 of the diffraction peak area showing the aluminum crystal structure attributed to the ⁇ -alumina (440) plane. That is, the diffraction peak area showing the crystal structure of the boehmite (020) plane measured by X-ray diffraction analysis is P1, the diffraction peak area showing the crystal structure of the (120) plane is P2, and the ⁇ -alumina (440) plane is assigned.
  • the diffraction peak area showing the aluminum crystal structure is P3, Of the values of (P1 / P3) ⁇ 100 (%) and (P2 / P3) ⁇ 100 (%), the larger value is less than 10%. If the boehmite structure is increased in the crystal of the support, it is not preferable because the physical properties of the support are difficult to control and the catalyst strength may be reduced.
  • Each diffraction peak area is calculated by fitting a graph obtained by X-ray diffraction analysis with an X-ray diffractometer using the least square method and correcting the baseline to obtain the height from the maximum peak value to the baseline ( Peak intensity W)
  • a peak width (half-value width) at a half value (1/2 W) of the obtained peak intensity was determined, and the product of this half-value width and peak intensity was defined as a diffraction peak area. From each of the obtained diffraction peak areas, “boehmite diffraction peak area / ⁇ -alumina diffraction peak area” was calculated.
  • baseline correction was performed with a TGS detector with a resolution of 4 cm ⁇ 1 , an integration count of 200, and a wave number range of 3000 to 4000 cm ⁇ 1 .
  • Absorbance was converted per unit mass.
  • Absorbance per unit mass (g ⁇ 1 ) Absorbance / Molded body mass
  • the wave number at the maximum peak position of the absorption spectrum corresponding to the acidic OH group is 3673 to in the range of 3678cm -1
  • wave number of the maximum peak position of the absorption spectrum due to the basic OH groups is in the range of 3770 ⁇ 3774cm -1.
  • ⁇ Measurement method of ignition loss The catalyst as the measurement sample was calcined at 570 ° C. for 2 hours, and calculated from the amount of mass reduction due to the calcining.
  • ⁇ Measurement method of peak temperature of desorbed water by temperature reduction method> In the temperature-reduction method, 0.05 g of catalyst sized to 250 to 710 ⁇ m was pretreated at 120 ° C. for 1 hour under the flow of helium gas using a catalyst analyzer (BEL CAT-A) manufactured by Nippon Bell. After the application, the gas was switched to hydrogen gas (99.99%) and the temperature was raised from 50 ° C. to 900 ° C. at 10 ° C./min.
  • FIG. 2 shows a graph as an example of the analysis result of the peak temperature of desorbed water by the temperature reduction method.
  • the horizontal axis represents temperature
  • the vertical axis represents the detection current of the quadrupole mass spectrometer.
  • Nitrogen monoxide adsorption is measured using a fully-automatic catalytic gas adsorption measuring device (manufactured by Okura Riken), and a mixed gas of helium gas and nitrogen monoxide gas (nitrogen monoxide concentration of 10) Volume%) was introduced in pulses, and the amount of adsorbed nitric oxide molecules per gram of the hydrotreating catalyst was measured. Specifically, about 0.02 g of the catalyst pulverized to 60 mesh or less was weighed, filled in a quartz cell, and the catalyst was heated to 360 ° C. to obtain 5 vol% hydrogen sulfide / 95 vol% hydrogen.
  • nitric oxide molecules were adsorbed at 50 ° C. with a mixed gas of helium gas and nitric oxide gas, and the amount of adsorbed nitric oxide molecules was measured.
  • Example 10 Preparation examples of ⁇ -alumina support, preparation examples of impregnation liquid, preparation examples of hydrotreating catalyst which is an embodiment of the present invention using each alumina support and impregnation liquid, and each alumina support and impregnation liquid were used.
  • a preparation example of a hydrotreating catalyst as a comparative example will be described below. First, preparation examples of the carrier will be described.
  • an aluminum sulfate aqueous solution was prepared by heating an aluminum sulfate aqueous solution obtained by diluting 14.29 kg of an aluminum sulfate aqueous solution having a concentration of 7% by mass in terms of Al 2 O 3 with 25.71 kg of ion exchange water to 60 ° C.
  • an aqueous aluminum sulfate solution was added thereto at a constant rate for 10 minutes to obtain Al 2 O 3 having a concentration of 3.8% by mass.
  • % Alumina hydrate slurry was prepared. At this time, the pH of the slurry was 7.2.
  • the alumina hydrate slurry was then aged at 60 ° C. for 60 minutes with stirring.
  • the aged alumina hydrate slurry was dehydrated and then washed with 1.5 L of an aqueous ammonia solution having a concentration of 0.3% by mass.
  • citric acid is added as a first organic compound in a 10% by mass solution. 0.60 kg was added, and then ammonia water having a concentration of 15% by mass was added to adjust the pH to 10.2, followed by aging at 95 ° C. for 10 hours while stirring.
  • ⁇ Preparation of carrier B> In a carrier prepared in the same manner as the carrier A, 0.60 kg of gluconic acid as a first organic compound in a 10% by mass solution and 0.30 kg of malic acid as a second organic compound in a 10% by mass solution are added. A carrier B was obtained.
  • ⁇ Preparation of carrier C> In a carrier prepared in the same manner as the carrier A, 1.20 kg of gluconic acid as a first organic compound in a 10% by mass solution and 0.30 kg of malic acid as a second organic compound in a 10% by mass solution are added. Carrier C was obtained.
  • ⁇ Preparation of carrier D> In a carrier prepared in the same manner as the carrier A, 0.60 kg of tartaric acid as a first organic compound in a 10% by mass solution and 0.30 kg of malic acid as a second organic compound in a 10% by mass solution are added, Carrier D was obtained.
  • ⁇ Preparation of carrier E> In a carrier prepared in the same manner as the carrier A, 0.60 kg of sucrose as a first organic compound in a 10% by mass solution and 0.30 kg of malic acid as a second organic compound in a 10% by mass solution are added, Carrier E was obtained.
  • ⁇ Preparation of carrier F> In a carrier prepared in the same manner as the carrier A, 0.60 kg of malic acid as a first organic compound in a 10% by mass solution and 0.30 kg of malic acid as a second organic compound in a 10% by mass solution are added. A carrier F was obtained.
  • ⁇ Preparation of carrier G> In a carrier prepared in the same manner as the carrier A, 1.50 kg of sucrose as a first organic compound in a 10% by mass solution and 0.30 kg of malic acid as a second organic compound in a 10% by mass solution are added, Carrier G was obtained.
  • ⁇ Preparation of carrier H> In the carrier prepared in the same manner as the carrier A, 0.60 kg of acetic acid as a first organic compound in a 10% by mass solution and 0.30 kg of malic acid as a second organic compound in a 10% by mass solution are added, Carrier H was obtained.
  • ⁇ Preparation of carrier I> In a carrier prepared in the same manner as the carrier A, 0.60 kg of gluconic acid as a first organic compound in a 10% by mass solution and 0.30 kg of citric acid as a second organic compound in a 10% by mass solution are added. Carrier I was obtained.
  • ⁇ Preparation of carrier J> In a carrier prepared in the same manner as the carrier A, 0.45 kg of gluconic acid as a first organic compound in a 10% by mass solution and 0.60 kg of citric acid as a second organic compound in a 10% by mass solution are added. A carrier J was obtained.
  • ⁇ Preparation of carrier K> In the carrier prepared in the same manner as the carrier A, the first organic compound and the second organic compound were not added at all, and the carrier K was obtained.
  • ⁇ Preparation of carrier L> In a carrier prepared in the same manner as in the preparation of Carrier A, 0.60 kg of citric acid as a first organic compound was added in a 10% by mass solution, and nothing was added to the second organic compound to obtain Carrier L.
  • ⁇ Preparation of carrier M> In the carrier prepared in the same manner as the carrier A, 1.80 kg of sucrose as a first organic compound in a 10% by mass solution and 0.30 kg of malic acid as a second organic compound in a 10% by mass solution were added. Other steps were carried out in the same manner as in the preparation of Carrier A to obtain Carrier M.
  • ⁇ Preparation of carrier N> The carrier A obtained in the same manner as the preparation of the carrier A was dried at 110 ° C. and then fired in an electric furnace at 700 ° C. for 3 hours to obtain a carrier N.
  • ⁇ Preparation of carrier O> The carrier A obtained in the same manner as the preparation of the carrier A was dried at 110 ° C. and then fired in an electric furnace at 350 ° C. for 3 hours to obtain a carrier O.
  • ⁇ Preparation of impregnation liquid> Next, an example of adjusting the impregnating liquid will be described.
  • ⁇ Preparation of impregnation liquid a> 255 g of molybdenum trioxide and 101 g of cobalt carbonate were suspended in 700 ml of ion-exchanged water, and this suspension was heated at 95 ° C. for 5 hours with an appropriate refluxing apparatus so that the liquid volume did not decrease. And 121 g of citric acid were added and dissolved to prepare impregnating solution a.
  • Example 1 Preparation of hydrotreating catalyst> After impregnating the carrier A with 1000 g of the impregnating liquid a, drying at 200 ° C., followed by further calcining in an electric furnace at 450 ° C. for 1 hour, the hydrotreating catalyst (hereinafter also simply referred to as “catalyst”. Examples below) The same applies to.
  • Examples 2 to 16 Preparation of hydrotreating catalyst> The types of the carrier prepared as described above (preparation example) and the type of impregnation liquid (preparation example) are combined as shown in Table 1 below. The catalyst of Example 16 was prepared.
  • each carrier in Examples 1 to 16 and Comparative Examples 1 to 8 obtained as described above is shown in Tables 1A and 1B
  • the properties of each catalyst are shown in Tables 2A and 2B.
  • the specific surface area represents the specific surface area of the catalyst.
  • the supported amount (% by mass) of each element is a catalyst standard value as described above.
  • the amount of carbon is also a catalyst standard value.
  • straight-run gas oil (density 0.8468 g / cm 3 at 15 ° C., sulfur content 1.13% by mass, nitrogen content 0.083% by mass) is supplied at a rate of 150 ml / hour into the fixed bed flow type reactor.
  • hydrodesulfurization treatment was performed and hydrorefining was performed.
  • the reaction conditions at that time are a hydrogen partial pressure of 4.5 MPa, a liquid space velocity of 1.0 h ⁇ 1 , and a hydrogen oil ratio of 250 Nm 3 / kl.
  • the reaction temperature was changed in the range of 300 to 385 ° C., sulfur analysis in the refined oil at each temperature was performed, and the temperature at which the sulfur content in the refined oil became 10 ppm was determined.
  • reaction rate constant was determined based on the following formula 1.
  • K n LHSV ⁇ 1 / (n ⁇ 1) ⁇ (1 / S n ⁇ 1 ⁇ 1 / S 0 n ⁇ 1 ) Equation 1 here, K n : Reaction rate constant n: The desulfurization reaction rate is proportional to the power of the sulfur concentration of the feedstock (1.5 for LGO) S: Sulfur concentration in treated oil (%) S 0 : Sulfur concentration (%) in the feedstock LHSV: Liquid space velocity (hr ⁇ 1 ) The results of the above confirmation test are shown in Table 3.
  • Examples 1 to 16 all have appropriate values regarding the properties of the catalyst.
  • the ratio of the OH group of the carrier exceeds the upper limit of 0.40
  • the catalyst surface area is lower than the lower limit of 200 m 2 / g
  • the catalyst The average pore diameter is not within the preferred range.
  • the ratio of the OH group of the support exceeds the upper limit of 0.40 and the average pore diameter is within the range of the appropriate value
  • the catalyst surface area is 200 m 2 which is the lower limit of the appropriate value. / G.
  • the crystal size of the support alumina precursor simultaneously exceeds 45% which is the upper limit of the appropriate value.
  • Comparative Example 3 although the catalyst surface area is high, the average pore diameter is below the lower limit of the appropriate value, so that it is not appropriate for loading of the active metal species, and the nitrogen monoxide adsorption amount is the lower limit of the appropriate value.
  • Comparative Example 5 is not preferable because the crystal form of the carrier alumina includes a state other than ⁇ .
  • the amount of supported active metal is not within the optimum range.
  • the loss on ignition greatly exceeds 5% by weight, which is the upper limit of the appropriate value, and the amount of carbon contained also exceeds 2% by weight, which is the upper limit of the appropriate value.
  • Example 1 the temperature at which the sulfur content in refined oil is 10 ppm, which is an indicator of catalyst performance, is 360 ° C. or less, and the above relative activity, which is an indicator of catalyst regeneration performance, is 80% or more. It is.
  • Comparative Examples 5 and 8 have poor catalyst regeneration performance
  • Comparative Examples 1 to 7 have poor catalyst performance
  • Comparative Example 5 has poor catalyst performance and catalyst regeneration performance.
  • the hydrocarbon oil hydrotreating catalyst (hereinafter also referred to as “the catalyst of the present invention”) according to the second embodiment of the present invention is a carrier (hereinafter referred to as an inorganic composite oxide carrier or a mixture of ⁇ -alumina and a foreign element metal). It is simply called a carrier) and an active metal component, and has a predetermined property.
  • an inorganic composite oxide carrier or a mixture of ⁇ -alumina and a foreign element metal
  • the active metal component has a predetermined property.
  • the properties of the inorganic composite oxide support, the active metal component and the catalyst will be described in detail below.
  • Examples of the inorganic composite oxide carrier that constitutes the hydrotreating catalyst include those that are used for known catalysts of this type and are made of various inorganic substances.
  • the inorganic composite oxide carrier is an inorganic composite oxide mainly composed of aluminum excluding impurities, and the crystal state of alumina can be classified as ⁇ -alumina.
  • Other inorganic components constituting the carrier are as follows: For example, various composite oxides composed of composite oxides with at least one selected from phosphorus, silica-titania, zirconia, boria, magnesia and the like can be raised.
  • the composite oxide includes aluminum and at least one element selected from phosphorus, silicon, titanium, zirconium, boron, and magnesium.
  • the composite oxide include, for example, aluminum-silicon, zeolite, aluminum-titanium, aluminum-phosphorus, aluminum-boron, aluminum-magnesium, aluminum-zirconium, aluminum-titanium-phosphorous, etc. It is not limited to these.
  • the properties and shape of the inorganic composite oxide support are appropriately selected according to various conditions such as the type and composition of the metal component to be supported and the application of the catalyst. In order to effectively support the active metal component in a highly dispersed state on the support and to ensure sufficient catalytic activity, a porous support is usually used and has a relatively small pore having a pore diameter of 500 mm or less. Are preferably used.
  • an appropriate binder component or additive can be contained in the formation of the support or catalyst body.
  • the catalyst support of the present invention corresponds to a basic OH group with respect to absorbance Sa of a spectral peak in the wave number range of 3673 to 3678 cm ⁇ 1 corresponding to an acidic OH group measured by a transmission Fourier transform infrared spectrophotometer.
  • the ratio Sb / Sa of the absorbance Sb of the spectral peak in the wave number range of 3770 to 3774 cm ⁇ 1 is in the range of 0.20 to 0.45.
  • the ratio Sb / Sa is more preferably in the range of 0.20 to 0.40.
  • Active metals are known to vary in dispersibility depending on the properties of the support surface, and when Sb / Sa is in the above range, high dispersibility of the active metal on the support surface is particularly noticeable.
  • the carrier of the present invention catalyst shows an example of light absorption spectrum comprising 3770 wavenumber range of ⁇ 3774cm -1 corresponding to the wave number range and basic OH groups of the acidic OH corresponding to the radical 3674 ⁇ 3678cm -1 Keep it.
  • FIG. 1 shows a light absorption spectrum related to a carrier in Examples described later. (1) to (4) correspond to carriers L, A2, F, and A, respectively.
  • the main component alumina undergoes a calcination step to prepare ⁇ -alumina via the pseudoboehmite crystal state, but the precursor alumina (before calcination)
  • the pseudoboehmite is characterized in that the crystallite diameter determined from the full width at half maximum of the XRD diffraction spectrum (020) peak is 15 to 40 mm. Control of the crystallite size of pseudoboehmite is important because it optimizes the pore structure of the inorganic composite oxide support and affects the difficulty of crystal transition by subsequent firing and the dispersibility of foreign elements.
  • the crystallite size exceeds 40 mm, the average pore diameter is large and the specific surface area is small, so that the performance of the catalyst may be lowered, which is not preferable.
  • a boehmite structure may remain in the crystal form of the alumina support, which may cause a concern that the stability of the catalyst performance may be impaired.
  • the dispersibility of the foreign element metal in the inorganic composite oxide carrier is low, which is not preferable because the effect of the foreign element metal is not sufficiently exhibited.
  • the crystallite size is less than 15 mm, the specific surface area is large and the dispersibility of the foreign element metal is high.
  • the inorganic composite oxide support used in the hydrocarbon oil hydrotreating catalyst related to the present invention for example, the content of aluminum or the like when using a composite oxide composed of aluminum and phosphorus, silicon, titanium or zirconium is described. To do.
  • the aluminum content in the carrier aluminum oxide (Al 2 O 3) (aluminum oxide (Al 2 O 3) 80 parts by mass or more in terms of per 100 parts by mass of the carrier) of 80% or more in terms of the preferred. If the aluminum content in terms of oxide is less than 80% by mass, the catalyst tends to be deteriorated quickly.
  • the content of phosphorus in the carrier, phosphorus oxide (P 2 O 5) converted at 5.0 wt% or less (phosphorus oxide relative to 100 parts by weight of carrier (P 2 O 5) converted at 5.0 parts by weight The following is preferable. If the phosphorus content is excessively large, the carrier pore distribution becomes broad, and the surface OH group ratio Sb / Sa falls below a predetermined range, so that the desulfurization performance tends to decrease.
  • silicon oxide (SiO 2) in terms of 3.0% by mass or less silicon oxide with respect to 100 parts by weight of carrier (SiO 2) 3.0 parts by weight or less in terms
  • SiO 2 silicon oxide with respect to 100 parts by weight of carrier (SiO 2) 3.0 parts by weight or less in terms
  • titanium oxide (TiO 2) 18.0% by weight in terms of the following (titanium oxide with respect to 100 parts by weight of carrier (TiO 2) 18.0 parts by mass or less in terms) are preferred . If the titanium content in terms of oxide is excessively large, desulfurization performance tends to be lowered because of insufficient support pore diameter and broad pore distribution.
  • zirconium oxide (ZrO 2) 9.0 wt% in terms of the following zirconium oxide with respect to 100 parts by weight of carrier (ZrO 2) 9.0 parts by weight or less in terms
  • zirconium content is excessively large, the carrier pore distribution becomes broad and the surface OH group ratio Sb / Sa exceeds the predetermined range, so that the desulfurization performance tends to be lowered.
  • the first metal component may be tungsten instead of molybdenum, or both molybdenum and tungsten.
  • the content (supported amount) of the first metal component should be 15 to 27% by mass in terms of oxide on the catalyst basis (15 to 27 parts by mass in terms of oxide with respect to 100 parts by mass of catalyst). It is.
  • the second metal component may be nickel instead of cobalt, or both cobalt and nickel.
  • the content (supported amount) of the second metal component must be 2 to 7% by mass in terms of oxide on the catalyst basis (2 to 7 parts by mass in terms of oxide with respect to 100 parts by mass of catalyst). It is.
  • the second metal component acts as a promoter for the first metal component, and when the content is less than 2% by mass in terms of oxide, the first metal component and the second metal component which are active metal components However, when it becomes difficult to maintain an appropriate structure and the content exceeds 7% by mass in terms of oxide, aggregation of the active metal component tends to proceed and the catalyst performance decreases.
  • an organic acid is usually contained in the impregnation liquid, and thus the organic acid becomes a carbon supply source supported on the alumina support.
  • the organic acid used for the active metal component include citric acid, malic acid, gluconic acid, tartaric acid, ethylenediaminetetraacetic acid (EDTA), and diethylenetriaminepentaacetic acid (DTPA), and more preferably citric acid and malic acid. , Tartaric acid, gluconic acid and the like.
  • organic acids for example, when using organic additives such as saccharides (monosaccharides, disaccharides, polysaccharides, etc.), in this specification, the content of carbon derived from organic acids refers to organic acids. And the content of carbon derived from both organic additives.
  • the catalyst of the present invention needs to have a specific surface area (SA) measured by the BET (Brunauer-Emmett-Teller) method in the range of 180 to 320 m 2 / g, and 190 m 2 / g or more. Preferably, 200 m 2 / g or more is more preferable. If the specific surface area (SA) is smaller than 180 m 2 / g, the metal components tend to aggregate and the desulfurization performance may be lowered, which is not preferable. On the other hand, when it is larger than 320 m 2 / g, the average pore diameter and pore volume are decreased, and the desulfurization activity tends to be lowered, which is not preferable.
  • SA specific surface area measured by the BET (Brunauer-Emmett-Teller) method in the range of 180 to 320 m 2 / g, and 190 m 2 / g or more. Preferably, 200 m 2 / g or more is more preferable. If
  • the average pore diameter must be 50 to 110 mm.
  • the average pore diameter is a value measured by a mercury intrusion method (mercury contact angle: 130 degrees, surface tension: 480 dyn / cm), and represents a pore diameter corresponding to 50% of the total pore volume.
  • the pore volume represents the volume of pores having a pore diameter of 41 mm or more. If the average pore size is less than 50%, the desulfurization performance may be reduced, and if the average pore size is greater than 110%, the catalyst strength may be reduced.
  • the catalyst of the present invention has an ignition loss (Ig Loss) of 5.0% by mass or less.
  • the ignition loss can be obtained by heating the catalyst at a high temperature as described in the item of the measurement method described later.
  • Ig Loss In order to reduce the ignition loss of the catalyst to 5.0% by mass or less, it is necessary to impregnate the inorganic composite oxide support with the impregnating solution and then calcinate, for example, at a temperature of 300 ° C. or higher.
  • By setting the loss on ignition of the catalyst to 5.0% by mass or less, when the desulfurization performance of a novel catalyst (fresh catalyst) having a novel activity during catalyst regeneration is 100%, it should be 85% or more. Can do.
  • the ignition loss of the catalyst increases.
  • the content of carbon derived from organic acid in the catalyst is 2.0% by mass or less based on the element basis on the catalyst basis, so that the desulfurization performance of an unused catalyst (fresh catalyst) with a novel activity during catalyst regeneration. When it is 100%, it can be 85% or more. If the carbon content is large, there is a concern that the active metal component aggregates due to the firing step during catalyst regeneration.
  • the catalyst of the present invention has a peak temperature of desorbed water in the range up to 450 ° C. (temperature at which the peak of the desorption spectrum of water appears) based on the catalyst temperature reduction method is 415 ° C. or lower. A specific example of the temperature reduction method will be described later.
  • the sulfidation treatment is performed on molybdenum with hydrogen sulfide or the like under a hydrogen stream, and the reaction requires oxygen to be desorbed from molybdenum oxide. Since the desorption peak of water is just the detection of desorption of oxygen from the molybdenum oxide as water, the progress of the sulfidation treatment and the reduction temperature of molybdenum are considered to have a correlation. Therefore, it is considered that the sulfurization treatment of molybdenum can be sufficiently advanced by lowering the peak temperature of the desorbed water.
  • the reduction temperature is too high, that is, if the peak temperature of the desorbed water is too high, there is a possibility that active metal aggregates exist because water interacts weakly with the composite oxide support. Get higher. For this reason, it is presumed that the sulfurization process does not proceed sufficiently. Therefore, it is necessary to reduce the reduction temperature and to reduce the interaction between water and the inorganic composite oxide carrier in order to highly disperse the active metal.
  • the desorbed water is mainly produced in the molybdenum reduction process, and its peak temperature varies depending on the carrier composition, active metal composition and the like.
  • peak temperature of desorption water peak temperature of desorption water
  • the amount of the active metal component is less than this range, the catalyst performance is insufficient, which is not preferable.
  • the amount of the active metal component is more than this range, it is not preferable because an aggregate of the active metal is generated and the dispersibility may be impaired. .
  • the adsorption amount of nitric oxide of the sulfurized catalyst is 8.0 ml / g or more.
  • the adsorption amount is more preferably 8.5 ml / g or more.
  • the reaction active point of the catalyst can be measured.
  • the reaction activity point of the catalyst is small and the effect of improving the catalyst performance cannot be obtained.
  • the amount of nitrogen monoxide adsorbed after sulfiding the catalyst varies depending on the physical and chemical characteristics of the support, the active metal composition, and the like. In order to perform adsorption of nitric oxide, a sulfidation treatment is required, and thus the reduction temperature of the active metal must be lowered to a certain temperature or lower.
  • the specific surface area (SA) of the inorganic composite oxide support is in the range of 180 to 320 m 2 / g; b) containing 80 to 98 parts by mass of aluminum in the inorganic composite oxide support in terms of alumina with respect to 100 parts by mass of the inorganic composite oxide support; c) The crystallite diameter determined from the half width of the XRD diffraction spectrum (020) peak of the pseudoboehmite of alumina as a main component in the carrier precursor is 15 to 40 mm, d) As an active metal component on the inorganic composite oxide support, at least one of molybdenum and tungsten is 15 to 27% by mass in terms of oxide, and at least one of cobalt and nickel is 2 to 7 in terms of oxide.
  • the ratio Sb / Sa of the absorbance Sb of the spectral peak in the wave number range of ⁇ 1 is in the range of 0.20 to 0.45, and the desorption peak temperature of water is 415 ° C. or lower.
  • the method for producing a hydrocarbon oil hydrotreating catalyst according to the present invention comprises: A first step of preparing (preparing) an inorganic composite oxide carrier; An impregnating solution comprising a first metal component that is at least one of molybdenum and tungsten, a second metal component that is at least one of cobalt and nickel, and an organic acid is prepared, and the first metal component And a second step of supporting the second metal component on the inorganic composite oxide support, A third step of obtaining a hydrotreating catalyst by heat-treating the alumina support carrying the first metal component and the second metal component obtained at the second step at a temperature of 100 to 600 ° C .; Have.
  • Step of obtaining an inorganic composite oxide slurry First, an aqueous solution of a basic metal salt and an aqueous solution of an acidic metal salt are mixed so that the pH is 6.5 to 9.5, preferably 6.5 to 8.5, more preferably 6.8 to 8.0. Thus, a hydrate of the inorganic composite oxide is obtained. At this time, the basic metal salt aqueous solution may contain a carboxylate. The inorganic composite oxide hydrate slurry is aged by a desired method (first aging step), and then washed to remove by-product salts to obtain a composite oxide slurry mainly composed of alumina.
  • the carboxylate used here is polyacrylic acid, hydroxypropyl cellulose, oxalic acid, malonic acid, succinic acid, glutaric acid, adipic acid, sebacic acid, maleic acid, gluconic acid, fumaric acid, phthalic acid, citric acid, etc. It is preferable to add in the range of 0.5 to 4.0 parts by mass with respect to 100 parts by mass of the composite oxide.
  • a hydrate of an inorganic composite oxide containing an element other than aluminum depending on the pH of the metal salt to be used, it is preliminarily mixed with an aqueous solution of an aluminum salt of an acidic aqueous solution or a basic aqueous solution, so that the pH falls within the above range. To obtain an inorganic composite oxide hydrate.
  • the basic aluminum salt sodium aluminate, potassium aluminate or the like is preferably used.
  • the acidic aluminum salt aluminum sulfate, aluminum chloride, aluminum nitrate and the like are preferably used, and the phosphate source includes phosphite ions, and includes ammonium phosphate, potassium phosphate, sodium phosphate, phosphorus Phosphate compounds that generate phosphate ions in water, such as acid and phosphorous acid, can be used.
  • the titanium mineral acid salt include titanium tetrachloride, titanium trichloride, titanium sulfate, titanyl sulfate, and titanium nitrate. In particular, titanium sulfate and titanyl sulfate are preferably used because they are inexpensive.
  • the temperature is usually kept at 40 to 90 ° C., preferably 50 to 70 ° C., and the temperature of this solution is ⁇ 5 ° C., preferably ⁇ 2 ° C., more preferably
  • the mixed aqueous solution heated to ⁇ 1 ° C. is usually 5 to 20 so that the pH is 6.5 to 9.5, preferably 6.5 to 8.5, more preferably 6.5 to 8.0. Minutes, preferably 7-15 minutes, to form a precipitate to obtain a slurry of hydrate.
  • the time required for the addition of the mixed aqueous solution to the basic metal salt aqueous solution is preferably 15 minutes or less because undesirable crystals such as bayerite and gibbsite may be generated in addition to pseudoboehmite as the time increases. 13 minutes or less is more desirable. Bayerite and gibbsite are not preferred because their specific surface area decreases when heat-treated.
  • Second aging process of inorganic composite oxide At least one organic compound (first organic compound) is added to the hydrate slurry obtained in the step 1-1, and the temperature is 30 ° C. or higher, preferably 80 to 100 in an aging tank equipped with a reflux. The aging is carried out at a temperature of, for example, 1 to 20 hours, preferably 2 to 10 hours (second aging step). In the first aging stage and the second aging stage, the inorganic composite oxide concentration is preferably less than 20% (20% by weight). ⁇ 1-3.
  • Kneading, molding and drying process >> The aged product obtained in the step 1-2 is put into a double-arm kneader with a steam jacket and heat-kneaded to obtain a moldable kneaded product, and then molded into a desired shape by extrusion molding or the like.
  • at least one second organic additive is added after being heated and concentrated until the concentration of the inorganic composite oxide becomes 20% (20% by weight) or more, and then further overheated. Good.
  • the timing of the addition of the second organic compound may be during the concentration of the aged product.
  • the molded product obtained in the 1-3 step is then heat-dried at, for example, 70 to 150 ° C., preferably 90 to 130 ° C., more preferably 400 to 800 ° C., preferably 400 to 600 ° C., for example 0 Calcination for 5 to 10 hours, preferably 2 to 5 hours, to obtain an alumina support.
  • at least 1 sort (s) chosen from organic acids or saccharides is preferable.
  • organic acids include citric acid, malic acid, tartaric acid, gluconic acid, acetic acid, ethylenediaminetetraacetic acid (EDTA), and diethylenetriaminepentaacetic acid (DTPA).
  • saccharide include monosaccharides, disaccharides and polysaccharides.
  • the addition amount is desirably in the range of 0.5 to 5.0 parts by mass with respect to 100 parts by mass of the inorganic composite oxide.
  • the addition amount is less than this range, it is difficult to obtain the effect due to the addition of the organic compound, and if it exceeds this range, the pore structure becomes too small due to the effect that is too strong, and the physical properties of the catalyst are not in the optimum range. This is not preferable because the efficiency of the preparation is deteriorated.
  • the OH group on the surface of the carrier is an important factor that affects the loading state, such as the dispersibility of the active metal species.
  • the control of the OH group can be performed everywhere in the carrier preparation step together with the composition of the inorganic composite oxide carrier and the crystallinity of the carrier alumina precursor.
  • ⁇ Second step> The impregnating liquid containing the first metal component, the second metal component, and the carbon component described above is brought into contact with the inorganic composite oxide support.
  • the raw material for the first metal component for example, molybdenum trioxide, ammonium molybdate, ammonium metatungstate, ammonium paratungstate, tungsten trioxide and the like are preferably used.
  • a raw material of a 2nd metal component nickel nitrate, nickel carbonate, cobalt nitrate, cobalt carbonate, etc. are used suitably.
  • orthophosphoric acid (hereinafter also simply referred to as “phosphoric acid”), ammonium dihydrogen phosphate, diammonium hydrogen phosphate, trimetaphosphoric acid, pyrophosphoric acid, tripolyphosphoric acid, etc. Used.
  • the impregnating solution is preferably made to have a pH of 4 or less using an organic acid to dissolve the metal component. When pH exceeds 4, it exists in the tendency for the stability of the metal component which melt
  • organic acid for example, citric acid, malic acid, tartaric acid, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA) can be used, and citric acid and malic acid are particularly preferably used.
  • organic additive saccharides (monosaccharide, disaccharide, polysaccharide, etc.) are used.
  • Organic additives such as 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 ) and the like may be added.
  • the carrier carrying the metal component obtained by contacting with the impregnating liquid in the second step is 100 to 600 ° C., preferably 110 to 600 ° C., more preferably 400 to 600 ° C., for 0.5 to 10 hours, preferably After heat treatment for 1 to 8 hours, the hydrotreating catalyst of the present invention is produced.
  • the firing temperature is excessively lower than 100 ° C., the operability due to residual moisture may be deteriorated, and the metal supporting state may be difficult to be uniform. If it exceeds 600 ° C., the metal causes aggregation and dispersion. Since there is a possibility that the maintenance effect cannot be expected, it is not preferable.
  • the organic compound (1st organic compound) is added to the slurry of a hydrate, and it heat-ages.
  • the crystallite diameter of the pseudoboehmite of alumina which is the precursor of the main component in the inorganic composite oxide can be reduced to 40 mm or less, and the specific surface area is optimized while optimizing the pore structure of the support. Can be increased.
  • the boehmite structure is less likely to remain in the crystal form, and the catalyst performance can be stabilized.
  • the dispersibility of the foreign element metal in the composite oxide carrier can be increased, which contributes to sufficiently exhibiting the effect of adding the foreign element metal.
  • the hydrocarbon oil to be desulfurized by the hydrotreating catalyst of the present invention is, for example, straight-run kerosene or straight-run light oil obtained from a crude oil atmospheric distillation device, straight-run heavy oil obtained from an atmospheric distillation device Hydrogenation of reduced pressure light oil or reduced pressure heavy light oil obtained by treating oil and residual oil with a vacuum distillation apparatus, catalytic cracked kerosene or contact cracked light oil obtained by catalytic cracking of desulfurized heavy oil, reduced pressure heavy light oil or desulfurized heavy oil Examples include hydrocracked kerosene or hydrocracked light oil obtained by cracking, pyrolyzed kerosene or pyrolyzed light oil obtained from a thermal cracking device such as a coker, and a fraction having a boiling point of 180 to 390 ° C.
  • the hydrogenation treatment using the catalyst is carried out under a high-temperature and high-pressure condition in a hydrogen atmosphere by filling the fixed bed reactor with the catalyst.
  • the hydrogen partial pressure is 3 to 8 MPa
  • the temperature is 260 to 420 ° C.
  • the liquid (hydrocarbon oil that is the liquid to be treated) space velocity is 0.3 to 5 hr ⁇ 1 .
  • carrier component alumina, phosphorus, silica, titania, zirconia
  • metal component mobdenum, cobalt, nickel, phosphorus
  • the content of each component was converted into an oxide conversion standard (Al 2 O 3 , P 2 O 5 , using an ICP apparatus (manufactured by Shimadzu Corporation, ICPS-8100, analysis software ICPS-8000). , SiO 2 , TiO 2 , ZrO 2 , MoO 3 , NiO, CoO).
  • ⁇ Alumina crystal state identification and crystallite size measurement method An X-ray diffractometer (manufactured by Rigaku Denki Co., Ltd .: RINT2100) was used, and the measurement sample was a compacted non-reflective plate for measurement as an observation sample, and the crystal state was measured by X-ray diffraction.
  • the crystallite size of the support alumina precursor was calculated by the Scherrer method from the (020) plane attributed to boehmite, and the crystal structure of the baked support was judged by comparing the diffraction peaks attributed to boehmite and ⁇ -alumina. .
  • Most of the inorganic composite oxide support of the present invention is preferably ⁇ -alumina.
  • the diffraction peak area P1 indicating the crystal structure of the boehmite (020) plane and the diffraction peak area P2 indicating the aluminum crystal structure attributed to the ⁇ -alumina (440) plane measured by X-ray diffraction analysis.
  • the ratio P2 / (P1 + P2) of P2 with respect to the total value of P1 and P2 needs to be 0.9 or more. It can also be said that P2 is 9 times or more than P1 (9 ⁇ (P2 / P1)). If the boehmite structure is increased in the crystal of the support, it is not preferable because the physical properties of the support are difficult to control and the catalyst strength may be reduced.
  • Each diffraction peak area is calculated by fitting a graph obtained by X-ray diffraction analysis with an X-ray diffractometer using the least square method and correcting the baseline to obtain the height from the maximum peak value to the baseline ( Peak intensity W)
  • a peak width (half-value width) at a half value (1/2 W) of the obtained peak intensity was determined, and the product of this half-value width and peak intensity was defined as a diffraction peak area. From each of the obtained diffraction peak areas, “boehmite diffraction peak area / ⁇ -alumina diffraction peak area” was calculated.
  • ⁇ Measurement method of carrier surface OH group> Using a transmission type Fourier transform infrared spectrometer (manufactured by JASCO Corporation: FT-IR / 6100), the maximum peak wave number of the acidic OH group, the absorbance at that wave number, the maximum peak of the basic OH group Wave number and absorbance at the wave number were measured. (Measurement method) 20 mg of a sample was filled in a molding container (inner diameter 20 mm ⁇ ) and compressed with 4 ton / cm 2 (39227 N / cm 2 ), and molded into a thin disk shape. This molded body was held at 500 ° C.
  • Absorbance per unit mass (g ⁇ 1 ) Absorbance / Molded body mass
  • the wave number of the maximum peak position of the absorption spectrum corresponding to the acidic OH group is 3673 to in the range of 3678cm -1
  • wave number of the maximum peak position of the absorption spectrum due to the basic OH groups is in the range of 3770 ⁇ 3774cm -1.
  • ⁇ Method for measuring specific surface area About 30 ml of a measurement sample was collected in a magnetic crucible (type B-2), heat-treated at 300 ° C. for 2 hours, then placed in a desiccator and cooled to room temperature to obtain a measurement sample. Next, 1 g of this sample was taken, and the specific surface area (m 2 / g) of the sample was measured by the BET method using a fully automatic surface area measuring device (manufactured by Yuasa Ionics Co., Ltd., Multisorb 12 type). ⁇ Measurement method of ignition loss> The catalyst as the measurement sample was calcined at 570 ° C. for 2 hours, and calculated from the amount of mass reduction due to the calcining.
  • ⁇ Measurement method of peak temperature of desorbed water by temperature reduction method> In the temperature-reduction method, 0.05 g of catalyst sized to 250 to 710 ⁇ m was pretreated at 120 ° C. for 1 hour under the flow of helium gas using a catalyst analyzer (BEL CAT-A) manufactured by Nippon Bell. After the application, the gas was switched to hydrogen gas (99.99%) and the temperature was raised from 50 ° C. to 900 ° C. at 10 ° C./min. The desorption spectrum of water at elevated temperature was measured with a quadrupole mass spectrometer (m / z: 18.34) manufactured by Pfeiffer Vacuum, and the desorption peak temperature of water was read from the obtained desorption spectrum. It was.
  • m / z: 18.34 quadrupole mass spectrometer
  • FIG. 2 shows a graph as an example of the analysis result of the peak temperature of desorbed water by the temperature reduction method.
  • the horizontal axis represents temperature
  • the vertical axis represents the detection current of the quadrupole mass spectrometer.
  • the solid line corresponds to Example 3 which will be described later
  • the dotted line corresponds to Comparative Example 5 which will be described later.
  • Nitrogen monoxide adsorption is measured using a fully-automatic catalytic gas adsorption measuring device (manufactured by Okura Riken), and a mixed gas of helium gas and nitrogen monoxide gas (nitrogen monoxide concentration of 10) Volume%) was introduced in pulses, and the amount of adsorbed nitric oxide molecules per gram of the hydrotreating catalyst was measured. Specifically, about 0.02 g of the catalyst pulverized to 60 mesh or less was weighed, filled in a quartz cell, and the catalyst was heated to 360 ° C. to obtain 5 vol% hydrogen sulfide / 95 vol% hydrogen.
  • nitric oxide molecules were adsorbed at 50 ° C. with a mixed gas of helium gas and nitric oxide gas, and the amount of adsorbed nitric oxide molecules was measured.
  • an aluminum sulfate aqueous solution was prepared by heating an aluminum sulfate aqueous solution obtained by diluting 11.37 kg of an aluminum sulfate aqueous solution of 7% by mass in terms of Al 2 O 3 concentration with 20.46 kg of ion exchange water to 60 ° C.
  • an aluminum sulfate aqueous solution was added at a constant speed for 10 minutes using a roller pump to prepare a hydrate slurry A containing phosphorus and alumina. .
  • the hydrate slurry was then aged at 60 ° C. for 60 minutes with stirring.
  • an aluminum sulfate aqueous solution was prepared by heating an aluminum sulfate aqueous solution obtained by diluting 11.61 kg of an aluminum sulfate aqueous solution of 7% by mass in terms of Al 2 O 3 concentration with 20.89 kg of ion exchange water to 60 ° C.
  • the aqueous solution of aluminum sulfate salt is added at a constant speed for 10 minutes using a roller pump to prepare a hydrate slurry B containing phosphorus and alumina. did.
  • Subsequent steps were carried out in the same manner as carrier A in Example 1, and carrier B was obtained.
  • an aluminum sulfate aqueous solution obtained by diluting 11.37 kg of an aluminum sulfate aqueous solution of 7% by mass in terms of Al 2 O 3 with 20.46 kg of ion-exchanged water, and 0.34 kg of titanium sulfate of 33% by mass in terms of TiO 2 concentration are ionized.
  • a titanium sulfate aqueous solution diluted to 2.25 kg with exchange water was mixed and heated to 60 ° C. to prepare an acidic mixed aqueous solution.
  • an aluminum sulfate aqueous solution obtained by diluting 10.71 kg of a 7% by mass aluminum sulfate aqueous solution in terms of Al 2 O 3 concentration with 19.29 kg of ion-exchanged water, and 0.76 kg of 33% by mass titanium sulfate in terms of TiO 2 concentration were ionized.
  • a titanium sulfate aqueous solution diluted to 5.00 kg with exchange water was mixed and heated to 60 ° C. to prepare an acidic mixed aqueous solution.
  • an aluminum sulfate aqueous solution obtained by diluting 9.64 kg of a 7% by mass aluminum sulfate aqueous solution in terms of Al 2 O 3 concentration with 17.36 kg of ion-exchanged water and 1.33 kg of 33% by mass titanium sulfate in terms of TiO 2 concentration were ionized.
  • a titanium sulfate aqueous solution diluted to 8.75 kg with exchange water was mixed and heated to 60 ° C. to prepare an acidic mixed aqueous solution.
  • an aluminum sulfate aqueous solution prepared by diluting 11.55 kg of an aluminum sulfate aqueous solution of 7% by mass in terms of Al 2 O 3 concentration with 20.79 kg of ion exchange water was mixed and heated to 60 ° C. to prepare an aluminum sulfate aqueous solution.
  • an aluminum sulfate aqueous solution is added at a constant speed for 10 minutes using a roller pump, and a hydrate slurry F containing phosphorus, silica and alumina is added. Prepared. Subsequent steps were carried out in the same manner as carrier A in Example 1, and carrier F was obtained.
  • an aluminum sulfate aqueous solution prepared by diluting 11.55 kg of an aluminum sulfate aqueous solution of 7% by mass in terms of Al 2 O 3 concentration with 20.79 kg of ion exchange water was mixed and heated to 60 ° C. to prepare an aluminum sulfate aqueous solution.
  • an aluminum sulfate aqueous solution was added at a constant speed for 10 minutes using a roller pump to prepare a hydrate slurry G containing silica and alumina. .
  • Subsequent steps were carried out in the same manner as carrier A in Example 1, and carrier G was obtained.
  • an aluminum sulfate aqueous solution obtained by diluting 10.48 kg of an aluminum sulfate aqueous solution of 7% by mass in terms of Al 2 O 3 with 18.86 kg of ion-exchanged water, and 0.76 kg of titanium sulfate of 33% by mass in terms of TiO 2 concentration are ionized.
  • a titanium sulfate aqueous solution diluted to 5.00 kg with exchange water was mixed and heated to 60 ° C. to prepare an acidic mixed aqueous solution.
  • the acidic mixed aqueous solution is added at a constant speed for 10 minutes using a roller pump, and the hydrate slurry H containing phosphorus, titania and alumina is added. Prepared. Subsequent steps were carried out in the same manner as carrier A in Example 1, and carrier H was obtained.
  • ⁇ Preparation of carrier I> a) A tank with a steam jacket having a capacity of 100 L (liter) was charged with 7.20 kg of a 22 mass% sodium aluminate aqueous solution in terms of Al 2 O 3 concentration, and diluted with 44.5 kg of ion-exchanged water. Next, 91.3 g of a sodium gluconate aqueous solution having a concentration of 26% by mass was added to this solution and heated to 60 ° C. with stirring to prepare a basic aluminum salt aqueous solution.
  • an aluminum sulfate aqueous solution obtained by diluting 11.31 kg of an aluminum sulfate aqueous solution of 7% by mass in terms of Al 2 O 3 concentration with 20.36 kg of ion-exchanged water and 0.69 kg of zirconium sulfate of 18% by mass in terms of ZrO 2 concentration were ionized.
  • An aqueous zirconium sulfate solution diluted to 2.50 kg with exchange water was mixed and heated to 60 ° C. to prepare an acidic mixed aqueous solution.
  • an aluminum sulfate aqueous solution obtained by diluting 10.83 kg of an aluminum sulfate aqueous solution of 7% by mass in terms of Al 2 O 3 with 19.50 kg of ion-exchanged water, and 0.38 kg of titanium sulfate of 33% by mass in terms of TiO 2 concentration are ionized.
  • a titanium sulfate aqueous solution diluted to 2.5 kg with exchange water and a zirconium sulfate aqueous solution obtained by diluting 0.42 kg of 18 mass% zirconium sulfate converted to ZrO 2 to 1.50 kg with ion exchange water were mixed and heated to 60 ° C. Then, an acidic mixed aqueous solution was prepared.
  • ⁇ Preparation of carrier B2> In the carrier prepared in the same manner as the carrier B, 0.13 kg of citric acid as a first organic compound was added in a 10% by mass solution. Other steps were carried out in the same manner as the preparation of the carrier B to obtain a carrier B2.
  • ⁇ Preparation of carrier B3> In the carrier prepared in the same manner as the carrier B, 0.50 kg of gluconic acid as a first organic compound was added in a 10% by mass solution. Other steps were carried out in the same manner as in the preparation of the carrier B to obtain a carrier B3.
  • ⁇ Preparation of carrier B4> In the carrier prepared in the same manner as the carrier B, 0.25 kg of malic acid as a first organic compound was added as a 10% by mass solution.
  • ⁇ Preparation of carrier C2> a) In a carrier prepared in the same manner as the carrier C, 0.50 kg of gluconic acid as a first organic compound in a 10% by mass solution is added, and then ammonia water having a concentration of 15% by mass is added to adjust the pH to 10. 3 and aged at 95 ° C. for 10 hours with stirring. d) The slurry after completion of the aging is dehydrated, heated while being kneaded with a double-arm kneader with a steam jacket, concentrated until the alumina concentration becomes 20% or more, and then 10% by mass of citric acid as the second organic compound. 0.25 kg was added, and the mixture was further heated and concentrated and kneaded to a predetermined moisture content. Other steps were carried out in the same manner as the preparation of the carrier C to obtain a carrier C2.
  • ⁇ Preparation of carrier A2> In the carrier prepared in the same manner as the carrier A, the first organic compound and the second organic compound were not added at all to obtain a carrier A2.
  • ⁇ Preparation of carrier A3> In the carrier prepared in the same manner as the carrier A, 1.25 kg of citric acid as a first organic compound in a 10% by mass solution was added. Other steps were carried out in the same manner as in the preparation of Carrier A to obtain Carrier A3.
  • ⁇ Preparation of carrier C3> The carrier C prepared in the same manner as the carrier C was dried at 110 ° C. and then fired in an electric furnace at 700 ° C. for 3 hours to obtain a carrier C3.
  • an aluminum sulfate aqueous solution in which 9.17 kg of an aluminum sulfate aqueous solution of 7% by mass in terms of Al 2 O 3 was diluted with 16.50 kg of ion-exchanged water, and 1.52 kg of titanium sulfate of 33% by mass in terms of TiO 2 were ionized.
  • a titanium sulfate aqueous solution diluted to 10.00 kg with exchange water was mixed and heated to 60 ° C. to prepare an acidic mixed aqueous solution.
  • the acidic mixed aqueous solution is added at a constant speed for 10 minutes using a roller pump, and the hydrate slurry K containing phosphorus, titania and alumina is added. Prepared. Subsequent steps were carried out in the same manner as carrier A in Example 1, and carrier K was obtained.
  • an aluminum sulfate aqueous solution prepared by diluting 11.07 kg of an aluminum sulfate aqueous solution of 7 mass% in terms of Al 2 O 3 concentration with 19.93 kg of ion exchange water was mixed and heated to 60 ° C. to prepare an aluminum sulfate aqueous solution.
  • an aluminum sulfate aqueous solution is added at a constant speed for 10 minutes using a roller pump, and a hydrate slurry L containing phosphorus, silica and alumina is added. Prepared. Subsequent steps were carried out in the same manner as carrier A in Example 1, and carrier L was obtained.
  • an aluminum sulfate aqueous solution was prepared by heating an aluminum sulfate aqueous solution obtained by diluting 10.95 kg of an aluminum sulfate aqueous solution of 7 mass% in terms of Al 2 O 3 concentration with 19.71 kg of ion exchange water to 60 ° C.
  • an aqueous aluminum sulfate salt solution is added at a constant speed for 10 minutes using a roller pump to prepare a hydrate slurry M containing phosphorus and alumina. did.
  • Subsequent steps were carried out in the same manner as carrier A in Example 1, and carrier M was obtained.
  • an aluminum sulfate aqueous solution was prepared by heating an aluminum sulfate aqueous solution in which 11.90 kg of an aluminum sulfate aqueous solution having a concentration of 7% by mass in terms of Al 2 O 3 was diluted with 21.43 kg of ion exchange water to 60 ° C. Next, while stirring the basic aluminum salt solution in the tank, an aqueous aluminum sulfate solution was added at a constant rate for 10 minutes using a roller pump to prepare an alumina hydrate slurry N. Subsequent steps were carried out in the same manner as carrier A in Example 1, and carrier N was obtained.
  • impregnating solution e ⁇ Preparation of impregnation liquid f> 156 g of molybdenum trioxide and 40 g of cobalt carbonate were suspended in 700 ml of ion-exchanged water, and this suspension was heated at 95 ° C. for 5 hours with an appropriate refluxing apparatus so that the liquid volume was not reduced. And 41 g of citric acid were added and dissolved to prepare impregnating solution f.
  • Example 1 Preparation of hydrotreating catalyst> After impregnating the carrier A with 1000 g of the impregnating liquid a, drying at 200 ° C., followed by further calcining in an electric furnace at 450 ° C. for 1 hour, the hydrotreating catalyst (hereinafter also simply referred to as “catalyst”. Examples below) The same applies to.
  • Example 2 to Example 19 Preparation of hydrotreating catalyst> The types of the carrier prepared as described above (preparation example) and the type of impregnation liquid (preparation example) are combined as shown in Table 1 below. The catalyst of Example 19 was prepared.
  • each carrier in Examples 1 to 19 and Comparative Examples 1 to 11 obtained as described above is shown in Tables 4A and 4B, and the properties of each catalyst are shown in Tables 5A and 5B.
  • the specific surface area represents the specific surface area of the catalyst.
  • the supported amount (% by mass) of each element is a catalyst standard value as described above.
  • the amount of carbon is also a catalyst standard value.
  • straight-run gas oil (density 0.8468 g / cm 3 at 15 ° C., sulfur content 1.13% by mass, nitrogen content 0.083% by mass) is supplied at a rate of 150 ml / hour into the fixed bed flow type reactor.
  • hydrodesulfurization treatment was performed and hydrorefining was performed.
  • the reaction conditions at that time are a hydrogen partial pressure of 4.5 MPa, a liquid space velocity of 1.0 h ⁇ 1 , and a hydrogen oil ratio of 250 Nm 3 / kl.
  • the reaction temperature was changed in the range of 300 to 385 ° C., sulfur analysis in the refined oil at each temperature was performed, and the temperature at which the sulfur content in the refined oil became 10 ppm was determined.
  • reaction rate constant was determined based on the following formula 1.
  • K n LHSV ⁇ 1 / (n ⁇ 1) ⁇ (1 / S n ⁇ 1 ⁇ 1 / S 0 n ⁇ 1 ) Equation 1 here, K n : Reaction rate constant n: The desulfurization reaction rate is proportional to the power of the sulfur concentration of the feedstock (1.5 for LGO) S: Sulfur concentration in treated oil (%) S 0 : Sulfur concentration (%) in the feedstock LHSV: Liquid space velocity (hr ⁇ 1 ) The results of the above confirmation test are shown in Tables 6A and 6B. Note that Tables 6A and 6B are shown side by side in Table 6 in consideration of the ease of grasping the data.
  • Comparative Examples 1 and 7 exceed the upper limit of 40 mm, and Comparative Examples 2 and 4 are lower than the lower limit of 15 mm.
  • the comparative examples 1 and 6 are less than 0.20 which is a minimum of an appropriate value, and the comparative examples 4 and 5 are over 0.45 which is an upper limit.
  • the crystal transition of alumina in Comparative Example 8, since the firing temperature of the support is below the lower limit of 400 ° C., which is a preferable temperature, the crystal form of the support alumina contains many boehmite forms and the ratio of ⁇ -alumina is small. .
  • the comparative examples 3 and 9 are less than 180 m ⁇ 2 > / g which is the minimum of a suitable value.
  • Comparative Example 2 is below the lower limit of the appropriate value of 50 mm, and Comparative Example 6 is higher than the upper limit of the appropriate value of 110 mm.
  • Comparative Examples 5, 6, 8, and 9 exceed the upper limit of 415 ° C., which is the upper limit of the appropriate value. 6 and 10 are below the lower limit of 8.0 ml / g which is the appropriate value.
  • Comparative Example 11 greatly exceeds the upper limit of 5.0% by mass, and Comparative Example 11 also contains the amount of carbon contained in the upper limit of the appropriate value. It exceeds 0% by mass.
  • the temperature at which the sulfur content in the refined oil is 10 ppm, which is an indicator of catalyst performance is 355 ° C. or less, and the above relative activity, which is an indicator of catalyst regeneration performance, is 85. % Or more.
  • Comparative Examples 1 to 10 have inferior catalyst performance
  • Comparative Example 11 has inferior catalyst regeneration performance. Comparative Examples 2, 8, and 9 are inferior not only in catalyst performance but also in catalyst regeneration performance.
  • the hydrodesulfurization catalyst of the present invention is extremely useful industrially because it can highly hydrodesulfurize hydrocarbon oils.

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