WO2016170995A1 - 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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WO2016170995A1
WO2016170995A1 PCT/JP2016/061453 JP2016061453W WO2016170995A1 WO 2016170995 A1 WO2016170995 A1 WO 2016170995A1 JP 2016061453 W JP2016061453 W JP 2016061453W WO 2016170995 A1 WO2016170995 A1 WO 2016170995A1
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catalyst
mass
parts
metal component
terms
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French (fr)
Japanese (ja)
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雄介 松元
渡部　光徳
雪子 中井
尚喜 岩▲崎▼
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日揮触媒化成株式会社
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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J27/00—Catalysts comprising the elements or compounds of halogens, sulfur, selenium, tellurium, phosphorus or nitrogen; Catalysts comprising carbon compounds
    • B01J27/14—Phosphorus; Compounds thereof
    • B01J27/186—Phosphorus; Compounds thereof with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J27/188—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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/08—Heat treatment
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/04—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used
    • C10G45/06—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof
    • C10G45/08—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing characterised by the catalyst used containing nickel or cobalt metal, or compounds thereof in combination with chromium, molybdenum, or tungsten metals, or compounds thereof

Definitions

  • the present invention relates to a hydrotreating catalyst for removing sulfur content in hydrocarbon oil in the presence of hydrogen, a production method thereof, and a hydrotreating method.
  • 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.
  • the hydrocarbon oil hydrotreating catalyst of the present invention is: (1) On the inorganic oxide support, as the active metal component, there is a first metal component that is at least one of molybdenum and tungsten, and a second metal component that is at least one of cobalt and nickel. Carried, (2) The content of the first metal component is 15 to 30 parts by mass in terms of oxide with respect to 100 parts by mass of the catalyst, and the content of the second metal component is relative to 100 parts by mass of the catalyst.
  • the specific surface area of the catalyst is 140 to 350 m 2 / g
  • the average pore diameter of the catalyst measured by mercury porosimetry is 50 to 130 mm
  • the amount of adsorption of nitrogen monoxide is 5.0% or less
  • the peak temperature of desorption water in the range up to 450 ° C is 415 ° C or less
  • the sulfurized catalyst is based on the temperature reduction method of the catalyst. Is 8.0 ml / g or more, It is characterized by that.
  • the inorganic oxide support contains 80 to 100 parts by mass of aluminum in terms of alumina with respect to 100 parts by mass of the inorganic oxide support.
  • the inorganic oxide carrier corresponds to at least one of the following (1) to (3). (1) With respect to 100 parts by mass of the inorganic oxide support, 5.0 parts by mass or less of phosphorus in terms of phosphoric acid is included. (2) The content of titanium is 20.0 parts by mass or less in terms of titania with respect to 100 parts by mass of the inorganic oxide support. (3) It contains 2.0 parts by mass or less of silicon in terms of silica with respect to 100 parts by mass of the inorganic oxide support.
  • the active metal component contains molybdenum and cobalt, and further contains 0 to 3.0 parts by mass in terms of oxide with respect to 100 parts by mass of the catalyst, at least one of nickel, copper, magnesium and zinc.
  • the maximum peak temperature of the desorbed water in the range up to 900 ° C. is 415 ° C. or less based on the temperature reduction method.
  • the method for producing a hydrocarbon oil hydrotreating catalyst of the present invention comprises: (1) preparing an inorganic oxide support containing aluminum; (2) preparing an impregnating solution containing a first metal component which is at least one of molybdenum and tungsten, a second metal component which is at least one of cobalt and nickel, and an organic acid, Supporting the metal component and the second metal component on the inorganic oxide carrier; (3) A hydrotreating catalyst obtained by heat-treating the inorganic oxide carrier carrying the first metal component and the second metal component obtained in the step (2) at a temperature of 100 to 600 ° C. Obtaining It is characterized by having.
  • the hydrocarbon oil hydrotreating method according to the present invention comprises a hydrogen partial pressure of 3 to 8 MPa, a temperature of 300 to 420 ° C., and a liquid space velocity of 0.3 to 5 hr ⁇ 1 in the presence of a hydrotreating catalyst. It is characterized by performing catalytic cracking of hydrocarbon oil.
  • the noble metal is expensive and has many problems when it is industrialized from the point of depletion. Therefore, in the present invention, by maintaining the high NO adsorption amount and appropriately controlling the reduction temperature of the catalyst, the sulfidation treatment is sufficiently advanced and the active metal is highly dispersed and can be easily regenerated. Can be obtained. Moreover, according to the method for producing a hydrocarbon oil hydrotreating catalyst of the present invention, the reduction peak temperature of the catalyst by hydrogen of the catalyst (the peak temperature of desorbed water based on the temperature rising reduction method).
  • hydrodesulfurization method of hydrocarbon oil with high desulfurization activity can be provided by using the hydrocarbon oil hydrotreating catalyst of the present invention.
  • the hydrocarbon oil hydrotreating catalyst of the present invention comprises, for example, an inorganic oxide carrier containing aluminum and an active metal component, and has predetermined properties.
  • an inorganic oxide carrier containing aluminum and an active metal component and has predetermined properties.
  • the properties of the inorganic oxide support, the active metal component, and the catalyst will be described in detail.
  • the inorganic oxide carrier that constitutes the hydrotreating catalyst include those that are used for known catalysts of this type and that are made of various inorganic substances.
  • the inorganic component or the inorganic component constituting the carrier include various composite oxides composed of alumina or at least one composite oxide selected from alumina and silica, phosphorus, boria, titania, zirconia, magnesia, and the like. Can be mentioned.
  • the composite oxide includes aluminum and at least one element selected from titanium, silicon, phosphorus, zirconium, magnesium, and boron.
  • the composite oxide include, but are not limited to, silica alumina, zeolite, alumina titania, alumina phosphorus, alumina boria, alumina magnesia, alumina zirconia, alumina titania silica, and the like.
  • the properties and shape of the inorganic 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.
  • a porous support is usually used, and relatively small pores having a pore diameter of 500 mm or less are used. What has is used suitably.
  • an appropriate binder component or additive can be contained in the formation of the support or catalyst body.
  • Examples of the inorganic oxide support (hereinafter also simply referred to as “support”) used in the hydrocarbon oil hydrotreating catalyst according to the present invention include, for example, aluminum single oxide or a composite composed of aluminum and silicon, phosphorus, or titanium. It describes about content, such as aluminum in the case of using an oxide.
  • 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.
  • titanium oxide (TiO 2) 20.0% by weight in terms of the following (titanium oxide with respect to 100 parts by weight of carrier (TiO 2) 20.0 parts by mass or less in terms) are preferred . If the titanium content in terms of oxide is excessively large, the carrier pore distribution becomes broad and the desulfurization activity tends to decrease.
  • 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) below 5.0 parts by terms ) is preferred.
  • the carrier pore distribution becomes broad and 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 must be 15 to 30% by mass in terms of oxide on the catalyst basis (15 to 30 parts by mass in terms of oxide with respect to 100 parts by mass of catalyst). It is.
  • the content of the first metal component is excessively less than 15% by mass in terms of oxide, the desulfurization activity necessary for the reaction may not be ensured. If it is excessively greater than 30% by mass, the metal component is likely to aggregate. Therefore, the dispersibility may be hindered.
  • the second metal component may be nickel instead of cobalt, or both cobalt and nickel.
  • the content (supported amount) of the second metal component should be 3 to 7% by mass in terms of oxide on the catalyst basis (15 to 30 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 3% 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.
  • the content of carbon derived from an organic acid is required to be 2.0% by mass or less on the catalyst basis as an element basis (2.0 parts by mass or less on an element basis with respect to 100 parts by mass of the catalyst).
  • an organic acid is usually contained in the impregnation liquid, and thus the organic acid is a source of carbon supported on the inorganic oxide support. .
  • the carbon content is 2.0% by mass or less based on the elemental basis, when the desulfurization performance of an unused catalyst (fresh catalyst) having a novel activity during catalyst regeneration is 100%, it is 80% or more. can do. If the carbon content is large, there is a concern that the active metal component aggregates due to the firing step during catalyst regeneration.
  • organic acid examples include citric acid, malic acid, gluconic acid, tartaric acid, ethylenediaminetetraacetic acid (EDTA), diethylenetriaminepentaacetic acid (DTPA), and more preferably citric acid, malic acid, tartaric acid, gluconic acid, and the like. Is mentioned.
  • 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 method in the range of 140 to 350 m 2 / g.
  • SA specific surface area measured by the BET method
  • the specific surface area (SA) is smaller than 140 m 2 / g, the metal components are likely to aggregate and the desulfurization performance may be deteriorated.
  • it is larger than 350 m 2 / g, the average pore diameter and the pore volume are decreased, and the desulfurization activity tends to decrease, which is not preferable.
  • the average pore diameter is 50 to 130 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 130%, the catalyst strength may be reduced.
  • the catalyst of the present invention has an ignition loss (Ig Loss) of 5.0% 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 loss on ignition of the catalyst to 5.0% or less, the desulfurization performance of an unused catalyst (fresh catalyst) having a novel activity during catalyst regeneration can be 80% or more when the desulfurization performance is 100%. it can.
  • 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 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, active water aggregates may exist because water interacts weakly with the inorganic oxide support. Get higher. For this reason, it is presumed that the sulfurization process does not proceed sufficiently. Therefore, it is necessary to lower the reduction temperature and reduce the interaction between water and the inorganic oxide 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.
  • one (one) is 15 to 30% by mass in terms of oxide, and at least one (one) of cobalt and nickel is required to be 3 to 7% by mass in terms of oxide.
  • the catalyst of the present invention has an adsorption amount of NO (nitrogen monoxide) of the sulfurized catalyst of 8.0 ml / g or more.
  • the adsorption amount is more preferably 8.3 ml / g or more, and still more preferably 9.0 ml / g or more. Based on the NO molecule adsorption amount, the reaction active point of the catalyst can be measured.
  • the amount of NO adsorption after sulfiding the catalyst varies depending on the carrier composition, active metal composition, etc., as with the peak temperature of the desorbed water.
  • sulfurization treatment is required, and therefore the reduction temperature of the active metal must be lowered to a certain temperature or lower.
  • the NO adsorption amount equal to or higher than 8.0 ml / g
  • at least one of molybdenum and tungsten is converted into oxide as an active metal component on the inorganic oxide support. It is important that 15-30% by mass of at least one of cobalt and nickel is 3-7% by mass in terms of oxide, and the desorption peak temperature of water is 415 ° C. or lower.
  • 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
  • the method for producing a hydrocarbon oil hydrotreating catalyst according to the present invention comprises: A first step of preparing an inorganic oxide support containing aluminum; 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 oxide support, A step of heat-treating the inorganic oxide support on which the first metal component and the second metal component are supported obtained in the second step at a temperature of 100 to 600 ° C. to obtain a hydrotreating catalyst; Have.
  • each step will be described.
  • 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.
  • a hydrate of inorganic oxide is obtained.
  • washing to remove by-product salts, hydrate containing other elements such as alumina or silicon other than alumina or alumina.
  • a slurry is obtained.
  • This hydrate slurry is further heated and aged, for example, and then heat-kneaded by conventional means, for example, to obtain a moldable kneaded product, and then molded into a desired shape by extrusion molding or the like, and then, for example, 70 to 150
  • the inorganic oxide is dried by heating at 90 ° C., preferably 90 to 130 ° C., and further preferably calcined at 400 to 800 ° C., preferably 450 to 600 ° C., for example, for 0.5 to 10 hours, preferably 2 to 5 hours.
  • a carrier is obtained.
  • an inorganic composite oxide hydrate 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, and then within the above pH 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 as the titanium mineral acid salt, titanium tetrachloride, titanium trichloride, titanium sulfate, titanyl sulfate, titanium nitrate and the like are exemplified.
  • titanium sulfate and titanyl sulfate are preferably used because they are inexpensive.
  • the phosphate source also includes phosphite ions, and phosphate compounds that generate phosphate ions in water, such as ammonia phosphate, potassium phosphate, sodium phosphate, phosphoric acid, phosphorous acid, etc. are used. Is possible.
  • 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.
  • ⁇ 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 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.
  • copper, magnesium or zinc is supported on an inorganic oxide carrier, for example, copper carbonate, magnesium carbonate, zinc carbonate or the like is used.
  • 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.
  • 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 105 to 550 ° C., more preferably 110 to 500 ° 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.
  • carrier component alumina, silica, phosphorus oxide, titania
  • metal component mobdenum, cobalt, nickel, copper, magnesium, phosphorus
  • the content of each component was converted into oxide conversion criteria (Al 2 O 3 , SiO 2 , P, using ICP device (manufactured by Shimadzu Corporation, ICPS-8100, analysis software ICPS-8000)). 2 O 5 , TiO 2 , MoO 3 , NiO, CoO, MgO, CuO).
  • ⁇ 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. 1 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.
  • a solid line (1) and a chain line (2) in FIG. 1A correspond to Examples 6 and 8 described later, respectively, and a solid line (3) and a chain line (4) in FIG. And 5.
  • the NO adsorption amount is measured using a fully-automatic catalytic gas adsorption amount measuring device (manufactured by Okura Riken), and pulsed with a mixed gas of helium gas and NO gas (NO concentration: 10% by volume) on the hydrotreated catalyst.
  • the amount of NO molecules adsorbed per 1 g 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.
  • Example 10 Preparation example of inorganic oxide support, preparation example of impregnation liquid, preparation example of hydrotreating catalyst which is an embodiment of the present invention using each inorganic oxide support and impregnation liquid, and each inorganic oxide support and impregnation
  • a preparation example of a hydrotreating catalyst which is a comparative example using a liquid is described below. First, preparation examples of the inorganic oxide support will be described.
  • ⁇ Preparation of inorganic oxide support A> A tank with a steam jacket with a capacity of 100 L (liter) was charged with 8.95 kg of a 22 mass% sodium aluminate aqueous solution in terms of Al 2 O 3 concentration, diluted with 33 kg of ion-exchanged water, and then converted into P 2 O 5 concentration. A 2.5 mass% sodium phosphate solution (5.40 kg) was added with stirring, and the mixture was heated to 60 ° C. to prepare a basic aqueous aluminum salt solution.
  • an acidic aluminum salt aqueous solution obtained by diluting 12.79 kg of an aluminum sulfate aqueous solution of 7% by mass in terms of Al 2 O 3 concentration with 23 kg of ion exchange water was heated to 60 ° C. Hydration containing phosphorus and alumina by adding acidic aluminum salt aqueous solution to tank containing basic aluminum salt aqueous solution at a constant rate using a roller pump until pH becomes 7.2 (addition time: 10 minutes).
  • Slurry A was prepared.
  • the obtained hydrate slurry A was aged at 60 ° C. for 1 hour with stirring, dehydrated using a flat plate filter, and further washed with 150 L of a 0.3 mass% aqueous ammonia solution.
  • the cake-like slurry after washing was diluted with ion-exchanged water so as to be 10% by mass in terms of Al 2 O 3 concentration, and then the pH was adjusted to 10.5 with 15% by mass ammonia water. This was transferred to an aging tank equipped with a reflux machine and aged at 95 ° C. for 10 hours with stirring.
  • the slurry after completion of aging was dehydrated and concentrated and kneaded to a predetermined moisture content while kneading with a double-arm kneader equipped with a steam jacket.
  • the obtained kneaded product was molded into a cylindrical shape having a diameter of 1.6 mm by an extrusion molding machine and dried at 110 ° C.
  • the dried molded product was baked in an electric furnace at a temperature of 500 ° C. for 3 hours to obtain a carrier A.
  • ⁇ Preparation of inorganic oxide support B> A tank with a steam jacket with a capacity of 100 L was charged with 9.23 kg of a 22 mass% sodium aluminate aqueous solution in terms of Al 2 O 3 concentration, diluted with 35 kg of ion-exchanged water, and then 2.5 in terms of P 2 O 5 concentration. 1.80 kg of a mass% sodium phosphate solution was added with stirring and heated to 60 ° C. to prepare a basic aluminum salt aqueous solution. Further, an acidic aluminum salt aqueous solution obtained by diluting 13.19 kg of an aluminum sulfate aqueous solution of 7% by mass in terms of Al 2 O 3 concentration with 24 kg of ion exchange water was heated to 60 ° C.
  • ⁇ Preparation of inorganic oxide support C> A tank with a steam jacket with a capacity of 100 L is charged with 9.38 kg of a 22 mass% sodium aluminate aqueous solution in terms of Al 2 O 3 concentration, diluted with 36 kg of ion-exchanged water, heated to 60 ° C., and basic. An aqueous aluminum salt solution was prepared. Further, it warmed an acidic aluminum salt aqueous solution obtained by diluting the concentration of Al 2 O 3 in terms of 7 wt% aqueous solution of aluminum sulfate 13.39kg with deionized water 24kg to 60 ° C..
  • ⁇ Preparation of inorganic oxide support D> A tank with a steam jacket with a capacity of 100 L is charged with 9.23 kg of a 22 mass% sodium aluminate aqueous solution in terms of Al 2 O 3 concentration, diluted with 36 kg of ion-exchanged water, heated to 60 ° C., and basic An aqueous aluminum salt solution was prepared.
  • ⁇ Preparation of inorganic oxide support E> A tank with a steam jacket with a capacity of 100 L is charged with 8.44 kg of a 22 mass% sodium aluminate aqueous solution in terms of Al 2 O 3 concentration, diluted with 35 kg of ion-exchanged water, heated to 60 ° C., and basic. An aqueous aluminum salt solution was prepared. Further, an acidic aluminum salt aqueous solution obtained by diluting 12.05 kg of a 7% by mass aluminum sulfate aqueous solution in terms of Al 2 O 3 concentration with 22 kg of ion-exchanged water, and 6 kg of 0.91 kg of 33% by mass titanium sulfate in terms of TiO 2 concentration.
  • the aqueous solution of titanium sulfate dissolved in the ion-exchanged water was mixed and heated to 60 ° C. to prepare a mixed aqueous solution.
  • Hydrate slurry containing titania and alumina by adding a mixed aqueous solution to a tank containing a basic aluminum salt aqueous solution at a constant rate using a roller pump until the pH becomes 7.2 (addition time: 10 minutes).
  • E was prepared. Subsequent steps were carried out in the same manner as carrier A in Example 1, and carrier E was obtained.
  • ⁇ Preparation of inorganic oxide support F> A tank with a capacity of 100 L and a steam jacket is charged with 7.50 kg of a 22 mass% sodium aluminate aqueous solution in terms of Al 2 O 3 concentration, diluted with 34 kg of ion-exchanged water, heated to 60 ° C., and basic An aqueous aluminum salt solution was prepared. 12 kg of an acidic aluminum salt aqueous solution obtained by diluting 10.71 kg of an aluminum sulfate aqueous solution of 7% by mass in terms of Al 2 O 3 with 19 kg of ion-exchanged water, and 12 kg of 1.82 kg of 33% by mass of titanium sulfate in terms of TiO 2 concentration.
  • the aqueous solution of titanium sulfate dissolved in the ion-exchanged water was mixed and heated to 60 ° C. to prepare a mixed aqueous solution.
  • Hydrate slurry containing titania and alumina by adding a mixed aqueous solution to a tank containing a basic aluminum salt aqueous solution at a constant rate using a roller pump until the pH becomes 7.2 (addition time: 10 minutes).
  • F was prepared.
  • Subsequent steps were carried out in the same manner as carrier A in Example 1, and carrier F was obtained.
  • ⁇ Preparation of inorganic oxide carrier G> In a tank with a 100 L steam jacket, 9.09 kg of 22 mass% sodium aluminate aqueous solution in terms of Al 2 O 3 concentration was added, diluted with 35 kg of ion-exchanged water, and then 2.5 in terms of P 2 O 5 concentration. 1.80 kg of a mass% sodium phosphate solution was added with stirring and heated to 60 ° C. to prepare a basic aluminum salt aqueous solution.
  • a titanium sulfate aqueous solution dissolved in 9 kg of ion exchange water was mixed and heated to 60 ° C. to prepare a mixed aqueous solution.
  • ⁇ Preparation of inorganic oxide support H> In a tank with a steam jacket of 100 L, 9.09 kg of 22 wt% sodium aluminate aqueous solution in terms of Al 2 O 3 concentration is added, diluted with 35 kg of ion-exchanged water, and then 5 wt% silicic acid in terms of SiO 2 concentration 0.90 kg of a sodium solution and 1.80 kg of a 2.5 mass% sodium phosphate solution in terms of P 2 O 5 concentration were added with stirring and heated to 60 ° C. to prepare a basic aluminum salt aqueous solution.
  • a mixed aqueous solution was prepared by heating an acidic aluminum salt aqueous solution obtained by diluting 12.99 kg of an aluminum sulfate aqueous solution of 7% by mass in terms of Al 2 O 3 concentration with 23 kg of ion-exchanged water to 60 ° C. Hydration containing phosphorus, silica and alumina by adding a mixed aqueous solution to a tank containing a basic aluminum salt aqueous solution at a constant rate using a roller pump until the pH is 7.2 (addition time: 10 minutes). Slurry H was prepared. Subsequent steps were carried out in the same manner as carrier A in Example 1, and carrier H was obtained.
  • ⁇ Preparation of inorganic oxide support I> A tank with a steam jacket with a capacity of 100 L is charged with 9.05 kg of 22 mass% sodium aluminate aqueous solution in terms of Al 2 O 3 concentration, diluted with 35 kg of ion-exchanged water, and then 5 mass% silicic acid in terms of SiO 2 concentration. 0.90 kg of a sodium solution and 1.80 kg of a 2.5 mass% sodium phosphate solution in terms of P 2 O 5 concentration were added with stirring and heated to 60 ° C. to prepare a basic aluminum salt aqueous solution.
  • a titanium sulfate aqueous solution dissolved in 9 kg of ion exchange water was mixed and heated to 60 ° C. to prepare a mixed aqueous solution.
  • a mixed aqueous solution is added to a tank containing a basic aqueous aluminum salt solution at a constant rate using a roller pump until the pH is 7.2 (addition time: 10 minutes), and contains silica, phosphorus, titania and alumina. Hydrate slurry I was prepared. Subsequent steps were carried out in the same manner as carrier A in Example 1, and carrier I was obtained.
  • ⁇ Preparation of inorganic oxide support J> A tank with a capacity of 100 L and a steam jacket is charged with 7.50 kg of a 22 mass% sodium aluminate aqueous solution in terms of Al 2 O 3 concentration, diluted with 34 kg of ion-exchanged water, heated to 60 ° C., and basic An aqueous aluminum salt solution was prepared. Also, 12 kg of an acidic aluminum salt aqueous solution obtained by diluting 10.71 kg of an aluminum sulfate aqueous solution of 7% by mass in terms of Al 2 O 3 with 19 kg of ion-exchanged water, and 12 kg of 1.80 kg of 33% by mass of titanium sulfate in terms of TiO 2 concentration.
  • the aqueous solution of titanium sulfate dissolved in the ion-exchanged water was mixed and heated to 60 ° C. to prepare a mixed aqueous solution.
  • Hydrate slurry containing titania and alumina by adding a mixed aqueous solution to a tank containing a basic aluminum salt aqueous solution at a constant rate using a roller pump until the pH becomes 7.2 (addition time: 10 minutes). J was prepared. Subsequent steps were carried out in the same manner as carrier A in Example 1, and carrier J was obtained.
  • ⁇ Preparation of inorganic oxide support K> A tank with a steam jacket with a capacity of 100 L is charged with 4.09 kg of 22 mass% sodium aluminate aqueous solution in terms of Al 2 O 3 concentration, diluted with 25 kg of ion-exchanged water, and then 5 mass% silicic acid in terms of SiO 2 concentration. 30.00 kg of sodium solution was added with stirring and heated to 60 ° C. to prepare a basic aluminum salt aqueous solution.
  • an acidic aluminum salt solution with the concentration of Al 2 O 3 in terms of 7 wt% aqueous solution of aluminum sulfate 8.57kg diluted with ion-exchanged water 15kg to 60 ° C. it was prepared a mixed aqueous solution.
  • ⁇ Preparation of inorganic oxide support L> A tank with a steam jacket with a capacity of 100 L is charged with 2.15 kg of 22 mass% sodium aluminate aqueous solution in terms of Al 2 O 3 concentration, diluted with 25 kg of ion-exchanged water, and then 5 mass% silicic acid in terms of SiO 2 concentration. 30.0 kg of sodium solution was added with stirring, and the mixture was heated to 60 ° C. to prepare a basic aluminum salt aqueous solution.
  • an acidic aluminum salt aqueous solution obtained by diluting 7.97 kg of an aluminum sulfate aqueous solution of 7% by mass in terms of Al 2 O 3 concentration with 7 kg of ion-exchanged water, and 2.27 kg of 33% by mass of titanium sulfate in terms of TiO 2 concentration are obtained.
  • a titanium sulfate aqueous solution dissolved in 1 kg of ion exchange water was mixed and heated to 60 ° C. to prepare a mixed aqueous solution.
  • ⁇ Preparation of inorganic oxide carrier M> The carrier A obtained in the same manner as in Example 1 was dried at 110 ° C. and then calcined in an electric furnace at 800 ° C. for 3 hours to obtain a carrier M.
  • Example 1 Preparation of hydrodesulfurization 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 17 Preparation of hydrodesulfurization catalyst>
  • the types of the prepared carrier (preparation example) and the impregnating liquid (preparation example) as described above are combined as shown in Table 1 below, and the other examples are performed in the same manner as in example 1.
  • the catalyst of Example 17 was prepared.
  • ⁇ Comparative Example 1 Preparation of hydrodesulfurization catalyst> The impregnating liquid e of Example 6 was used as the impregnating liquid and spray impregnated on 1000 g of the carrier C prepared in Example 5, and then dried at 120 ° C. to obtain a hydrotreating catalyst without firing.
  • ⁇ Comparative Example 2 Preparation of hydrodesulfurization catalyst> The impregnating liquid e of Example 6 was used as the impregnating liquid and spray impregnated on 1000 g of the carrier B prepared in Example 3, and then dried at 120 ° C.
  • Comparative Example 10 Preparation of hydrodesulfurization catalyst The types of the prepared carrier (preparation example) and the impregnating liquid (preparation example) as described above are combined as shown in Table 1 below, and the others are the same as in Example 1, and Comparative Examples 3 to 3 are compared. The catalyst of Example 10 was prepared.
  • each carrier in Examples 1 to 17 and Comparative Examples 1 to 10 obtained as described above are shown in Table 1, and the properties of each catalyst are shown in Table 2.
  • the specific surface area represents the specific surface area of the catalyst.
  • the loading amount (% by mass) of each element is a catalyst standard value as described above.
  • the supported amounts of Ni, Cu, and Mg oxides in Table 2 are shown in the column on the right side of the column displaying oxides.
  • 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 was 8 ppm was determined.
  • the performance calculation method after reproduction is as follows.
  • the reaction rate constant was obtained from the Arrhenius plot, and the regeneration rate from the fresh catalyst (unused catalyst) was calculated. Specifically, hydrogen sulfide was passed under the conditions described in (1) above after hydrogen sulfide was passed therethrough. From the change in the sulfur concentration in the hydrocarbon oil before and after passing through the reactor, the reaction rate constant was determined based on the following formula 1.
  • the ratio of the reaction rate constant (Kn) of the regenerated catalyst to the reaction rate constant (K n0 ) of the unused catalyst expressed as a percentage ((K n / K n0 ) ⁇ 100 [%]) is expressed as relative activity. It was.
  • 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 17 all have appropriate values regarding the properties of the catalyst.
  • the peak temperature of the desorption water exceeds 415 ° C., which is the upper limit of the appropriate value
  • the ignition loss greatly exceeds 5% by weight, which is the upper limit of the appropriate value.
  • the amount of carbon contained exceeds 2% by weight which is the upper limit of the appropriate value.
  • the peak temperature of desorption water at 450 ° C. or less and 900 ° C. or less exceeds 415 ° C.
  • Comparative Example 5 the peak temperature of desorption water at 900 ° C. or less exceeds 415 ° C. Yes.
  • Comparative Examples 4 and 7 the NO adsorption amount is lower than the lower limit of 8.0 ml / g, and Comparative Examples 8 and 9 are peak temperatures of desorbed water at 450 ° C. or lower and 900 ° C. or lower, respectively. Is over 415 ° C., and the NO adsorption amount is less than 8.0 ml / g.
  • Example 1 the temperature at which the sulfur content in the refined oil is 8 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.
  • Comparative Examples 1 and 2 have poor catalyst regeneration performance
  • Comparative Examples 4 to 10 have poor catalyst performance
  • Comparative Example 3 has poor catalyst performance and 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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