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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
  • 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
• • 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
• • 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
  • 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
  • B01J37/02—Impregnation, coating or precipitation
  • B01J37/03—Precipitation; Co-precipitation
  • B01J37/036—Precipitation; Co-precipitation to form a gel or a cogel
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B33/00—Silicon; Compounds thereof
  • C01B33/20—Silicates
  • C01B33/26—Aluminium-containing silicates, i.e. silico-aluminates
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01B—NON-METALLIC ELEMENTS; COMPOUNDS THEREOF; METALLOIDS OR COMPOUNDS THEREOF NOT COVERED BY SUBCLASS C01C
  • C01B35/00—Boron; Compounds thereof
  • C01B35/08—Compounds containing boron and nitrogen, phosphorus, oxygen, sulfur, selenium or tellurium
  • C01B35/10—Compounds containing boron and oxygen
• • C—CHEMISTRY; METALLURGY
  • C01—INORGANIC CHEMISTRY
  • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
  • C01G23/00—Compounds of titanium
  • C01G23/003—Titanates
• • 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
• • 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
  • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
  • B01J21/063—Titanium; Oxides or hydroxides thereof
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
  • B01J21/12—Silica and 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
  • B01J2523/00—Constitutive chemical elements of heterogeneous 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
  • 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
  • B01J35/63—Pore volume
  • B01J35/635—0.5-1.0 ml/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
  • B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
• • 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

Definitions

• the present invention relates to a hydrotreating catalyst support, a method for producing the same, a hydrotreating catalyst, and a method for producing the same.
• a catalyst in which an active metal component selected from Group VIA of the periodic table and Group VIII of the periodic table is supported on an alumina carrier has been widely used as a hydrotreating catalyst for hydrocarbon oil.
• various hydrotreating catalysts containing silica, phosphorus oxide, or the like as a third component have been proposed.
• US Pat. No. 6,057,049 contains 5-50% by weight Al 2 O 3 , 10-90% by weight SiO 2 , and 5-40% by weight P 2 O 5 as catalysts used in the hydrocarbon conversion process.
• a catalyst composite composed of an amorphous solid solution of phosphorus, silicon, and aluminum oxide containing is described. Also, in the steps of making a mixture of alumina hydrosol, silica hydrosol and phosphorus compound, gelling the mixture to make particles, and calcining those particles to make phosphorus, silicon and aluminum oxides.
• a method for preparing the catalyst composite is also disclosed, both of which are mixed in the form of a sol and then gelled.
• Patent Document 2 discloses that Group VIII non-noble metal oxide 2.5 to 6% by mass, Group VIB metal oxide 13 to 24% by mass, silica 0 to 2% by mass, and phosphorus oxide 0 to A total surface area of 170-220 m 2 / g carrying 2% by weight, a total pore volume of 0.6-0.8 cm 3 / g, and less than about 33% of the total pore volume is less than about 100 mm in diameter primary Present as micropores, such that at least about 41% of the total pore volume exists as secondary micropores with a diameter of about 100-200 mm, and about 16-26% of the total pore volume exists as mesopores with a diameter ⁇ 200 mm.
• a method is described in which a hydrocarbon raw material is supplied in the presence of a catalyst of a porous alumina carrier having a pore size distribution and hydrotreated.
• Patent Document 3 an aqueous solution of an aluminum salt containing phosphate ions in which silica hydrogel is suspended and a neutralizing agent mixed with water so as to have a pH of 6.5 to 8.5. After obtaining a hydrate and washing the hydrate, it is molded, dried, and calcined to have a high effective pore volume ratio, a high specific surface area, excellent strength, and improved desulfurization activity and decomposition activity. The obtained catalyst is disclosed.
• Patent Document 4 a composite oxide support composed of alumina and one or more oxides selected from silica, titania, phosphorous oxide, boria, zirconia, ceria and magnesia, and a periodic table.
• a hydrodesulfurization catalyst comprising a sulfide of a group VIA metal, a sulfide of a metal of group VIII of the periodic table and a carbonaceous material is disclosed.
• a sodium aluminate aqueous solution containing sodium gluconate and an aluminum sulfate aqueous solution are mixed and aged, washed with warm water, silica sol is added, and then a silica-alumina carrier is prepared by aging, kneading and the like. Yes. It is disclosed that when this carrier is used, a ratio of a high acid amount of ammonia adsorption heat is decreased, and a catalyst in which a decrease in liquid yield and a decrease in activity due to excessive decomposition are suppressed can be obtained.
• Patent Document 5 discloses a hydrodesulfurization catalyst in which at least one metal selected from Group VIA and Group VIII of the Periodic Table is supported on a silica-titania-alumina support.
• a high-performance catalyst is disclosed in which the effective pore volume does not decrease even when the amount of titania is increased by setting the peak area to 1 ⁇ 4 or less of the peak area of ⁇ -alumina.
• Patent Document 6 uses a solution containing a compound containing at least one selected from Group 8 metals of a periodic table, a molybdenum compound, a phosphorus compound, and an organic acid on an inorganic oxide support containing a phosphorus oxide.
• a method for producing a hydrotreating catalyst containing a predetermined amount of Group 8 metal and phosphorus oxide in terms of oxide and containing a predetermined amount of carbon derived from an organic acid is disclosed.
• an inorganic oxide carrier containing a phosphorus oxide is prepared by kneading an inorganic oxide raw material and a phosphorus oxide raw material.
• the resulting catalyst can reduce sulfur compounds and nitrogen compounds in hydrocarbon oils as compared to conventional catalysts.
• the inorganic oxide contains alumina as a main component and contains at least one selected from zeolite, boria, silica and zirconia.
• Patent Document 7 discloses that on a carrier containing 0.1 to 10% by mass of titanium atom in terms of oxide and 10% by mass or less of phosphorus oxide on the basis of carrier, at least one selected from Group VIA of the periodic table and a period of A catalyst is disclosed in which a predetermined amount of at least one selected from Group VIII metals, carbons derived from organic acids, and phosphorus oxides are supported. At this time, it is reported that the catalyst is excellent in the effect of reducing sulfur compounds and nitrogen compounds in hydrocarbon oil.
• various alumina gels can be used as the raw alumina amount, and powders of various oxide components can be used as the other oxide components. Specifically, it is described that an alumina gel, a solution of titanium oxide or a titanium compound, and a raw material of phosphorus oxide are kneaded.
• An object of the present invention is to provide a support for a hydrotreating catalyst from which a hydrotreating catalyst having excellent desulfurization activity (hydrogenation activity) can be obtained, a method for producing the same, a hydrotreating catalyst, and a method for producing the same.
• alumina and the first oxide are prepared.
• the composite oxide gel containing the component is prepared, and then the carrier prepared by adding the second oxide component becomes a catalyst in which the supported active metal component is in the form of fine particles and is highly dispersed.
• the present invention provides a support for a hydrotreating catalyst as shown below, a method for producing the same, a hydrotreating catalyst, and a method for producing the same.
• a support for a hydrotreating catalyst made of an alumina-based composite oxide, per carrier unit surface area caused by acidic OH groups measured by a transmission type Fourier transform infrared absorption spectrum measuring device (FT-IR)
• FT-IR transmission type Fourier transform infrared absorption spectrum measuring device
• the absorbance (OH AS ) is in the range of 0.04 to 0.1 m ⁇ 2
• the absorbance (OH BS ) per unit surface area of the carrier due to the basic OH group measured by the FT-IR is 0.01 to
• the wave number of the maximum peak position of the absorption spectrum due to the acidic OH group is in the range of 3670 to 3695 cm ⁇ 1
• the wave number of the maximum peak position of the absorption spectrum due to the basic OH group is 3760 to 3780 cm ⁇ In the range of 1 .
• the ratio (OH BS ) / (OH AS ) of the absorbance (OH BS ) of the basic OH group to the absorbance (OH AS ) of the acidic OH group is in the range of 0.2 to 0.5.
• the absorbance (OH AW ) of the acidic OH group per unit mass of the carrier is in the range of 10 to 30 g ⁇ 1
• the absorbance (OH BW ) of the basic OH group per unit mass of the carrier is 4 to
• the ratio (OH BW ) / (OH AW ) of the absorbance (OH BW ) of the basic OH group and the absorbance (OH AW ) of the acidic OH group is 0.2 in the range of 6.5 g ⁇ 1.
• the alumina-based composite oxide includes alumina, a first oxide other than alumina, and a second oxide other than alumina, and the first oxide is at least one selected from Si, Ti, and Zr.
• the content of the first oxide is in the range of 1 to 10% by mass based on the alumina-based composite oxide, and the content of the second oxide is 1 to 5 based on the alumina-based composite oxide.
• the carrier for hydrotreating catalyst according to the above (4) characterized in that it is in the range of mass%, and the content of alumina is in the range of 85 to 98 mass% based on the alumina-based composite oxide.
• the pore volume (PV) of the carrier is in the range of 0.5 to 1.5 mL / g, and the average pore diameter (D P ) of the carrier is in the range of 60 to 150 mm.
• the hydrotreating catalyst support according to any one of (1) to (6) above, wherein at least one element selected from Group VIA of the periodic table and at least selected from Group VIII of the periodic table A hydrotreating catalyst characterized by supporting one kind of element.
• the element selected from Group VIA of the periodic table is any of Cr, Mo, and W, and the element selected from Group VIII of the periodic table is any of Co or Ni
• the amount of the Group VIA element of the periodic table (in oxide equivalent) is in the range of 10 to 60 parts by mass with respect to 100 parts by mass of the carrier (in oxide equivalent);
• a method for producing a hydrotreating catalyst support as described in (4) or (5) above, comprising an alkali aluminate aqueous solution (A solution), an aluminum salt aqueous solution, and the first oxide metal salt A slurry preparation step A in which a mixed oxide hydrogel (hydrate) slurry is prepared by mixing a mixed aqueous solution (solution B) with an aqueous solution, and the metal salt for the second oxide in the step or after the step.
• a method for producing a carrier for a hydrotreating catalyst comprising performing a step of adding a metal salt for a second oxide to be added.
• carrier for hydroprocessing catalysts characterized by performing the metal salt addition process for the 1st oxide to add.
• the supported active metal component becomes a finely dispersed catalyst in the form of fine particles, so that the degree of sulfidation when pre-sulfurized before the reaction is improved and hydrogen having excellent desulfurization activity is obtained.
• a chemical treatment catalyst can be provided.
• the above-described support can be easily produced.
• the catalyst can be easily produced.
• the carrier for hydrotreating catalyst according to the present invention (hereinafter also simply referred to as “the present carrier”) is made of an alumina-based composite oxide, and measured with a transmission type Fourier transform infrared absorption spectrum measuring apparatus (FT-IR).
• FT-IR Fourier transform infrared absorption spectrum measuring apparatus
• the absorbance per unit surface area of the carrier due to the acidic OH group (OH AS ) and the absorbance per unit surface area of the carrier due to the basic OH group measured by FT-IR (OH BS ) are within a predetermined range. It is necessary.
• OH AS is in the range of 0.04 to 0.1 m ⁇ 2
• OH BS is in the range of 0.01 to 0.02 m ⁇ 2
• OH AS and OH BS are By being in this range, the dispersibility of the active metal on the surface of the catalyst carrier is improved, and the desulfurization performance is greatly improved.
• the wave number of the maximum peak position of the absorption spectrum due to the acidic OH group is in the range of 3670 to 3695 cm ⁇ 1
• the wave number of the maximum peak position of the absorption spectrum due to the basic OH group is 3760 to 3780 cm ⁇ . It is in the range of 1 .
• the measurement method using FT-IR will be described later.
• the ratio of OH BS to OH AS (OH BS ) / (OH AS ) is in the range of 0.2 to 0.5, and the specific surface area of the carrier is in the range of 250 to 500 m 2 / g, This is preferable because the dispersibility of the active metal on the surface of the carrier is further improved.
• the absorbance (OH AW ) of the acidic OH group per unit mass of the carrier is in the range of 10 to 30 g ⁇ 1
• the absorbance (OH BW ) of the basic OH group per unit mass of the carrier is 4 to 6 in the range of .5G -1
• the ratio of the OH BW and OH AW (OH BW) / ( OH AW) is in the range of 0.2-0.5
• the dispersibility of the active metal in the support surface Since it improves further, it is preferable.
• the above-mentioned alumina-based composite oxide is preferably composed of alumina, a first oxide other than alumina, and a second oxide other than alumina.
• the first oxide is an oxide of at least one element selected from Si, Ti, and Zr
• the second oxide is an oxidation of at least one element selected from B and P
• the metal component to be supported later can be supported in a highly dispersed state, and a catalyst having a high activity and a long life can be obtained.
• the content of the first oxide is in the range of 1 to 10% by mass based on the above-mentioned alumina-based composite oxide, the metal component to be supported later can be supported in a higher dispersion state, and the activity is higher.
• the metal component to be supported later is highly dispersed. This is preferable because it can be supported in a state and a catalyst having higher activity and a longer life can be obtained.
• the alumina content is preferably in the range of 80 to 98% by mass based on the alumina-based composite oxide.
• the pore volume (PV) of the carrier is preferably in the range of 0.5 to 1.5 mL / g.
• the metal component can be supported in a highly dispersed state, and the hydrocarbon oil is more easily diffused when used as a hydrogenation catalyst.
• the strength of the carrier and the catalyst (molded body) is further improved.
• the average pore diameter (D P ) of the support is preferably in the range of 60 to 150 mm from the viewpoint of the specific surface area of the catalyst and the diffusion of the hydrocarbon oil.
• the average pore diameter is 60 mm or more, the hydrocarbon oil is more easily diffused when the hydrogenation catalyst is used.
• the strength of the carrier and the catalyst (molded product) is further improved. The method for measuring the pore volume and the average pore diameter will be described later.
• a mixed oxide is prepared by mixing an alkali aluminate aqueous solution (liquid A), a mixed aqueous solution (liquid B) of an aluminum salt aqueous solution and the above-described metal salt aqueous solution for the first oxide.
• a slurry preparation step A for preparing a hydrogel (hydrate) slurry, and a second oxide metal salt addition step in which the above-described second oxide metal salt is added in the step or after the step are performed.
• the carrier can be easily produced by carrying out the following steps. Details of the first manufacturing method will be described in the examples described later.
• a mixed oxide hydrogel (hydrate) slurry is prepared by mixing an alkali aluminate aqueous solution (liquid A) and a mixed aqueous solution (liquid B) of an aluminum salt aqueous solution and a metal salt aqueous solution for the first oxide.
• Step (Slurry Preparation Step A) B) Aging step (first aging step) (C) Cleaning step (d) Aging step (second aging step) (E) Step of kneading and concentrating (first kneading step) (F) Kneading step (second kneading step) (G) Step of molding (h) Step of heat treatment (drying and firing) (i) Step of adding an aqueous metal salt (for example, oxoacid salt) solution for the second oxide
• aqueous metal salt for example, oxoacid salt
• step (i) may be performed in at least one of the steps (a) to (e) or after at least one of the steps (a) to (e). May be.
• an alkali aluminate aqueous solution (liquid A) and a mixed aqueous solution (liquid C) of an aluminum salt aqueous solution and a metal salt aqueous solution for the second oxide are mixed to form a composite oxide hydrogel ( Hydrate)
• a slurry preparation step B for preparing a slurry and a metal salt addition step for the first oxide in which the metal salt for the first oxide is added in the step or after the step are performed.
• the carrier can be easily produced by carrying out the following steps. Details of the second manufacturing method will be described in the examples described later.
• step (r) may be performed in at least one of the steps (j) to (n), or after at least one of the steps (j) to (n). May be.
• the alkali aluminate aqueous solution (liquid A) in the slurry preparation step A or the slurry preparation step B contains a carboxylate
• the particles of alumina gel This is preferable in that the growth can be controlled and a carrier (catalyst) having a large specific surface area can be prepared.
• the above-described hydrotreating catalyst support supports at least one element selected from Group VIA of the periodic table and at least one element selected from Group VIII of the periodic table to thereby carry out the hydroprocessing of the present invention.
• a catalyst (hereinafter also referred to as “the present catalyst”) can be obtained.
• the element selected from Group VIA of the periodic table is preferably Cr, Mo, or W from the viewpoint of hydrodesulfurization activity, and the element selected from Group VIII of the periodic table is Co. Or Ni is preferred from the viewpoint of hydrodesulfurization activity.
• the supported amount of the VIA group element (as oxide) in the range of 10 to 60 parts by mass with respect to 100 parts by mass of the carrier (as oxide) is the desulfurization activity and catalyst life.
• the supported amount of the Group VIII element in the periodic table (in oxide equivalent) is in the range of 1 to 20 parts by mass with respect to 100 parts by mass of the present support (in oxide equivalent). More preferable from the viewpoint.
• the catalyst impregnates the support with an aqueous solution containing at least one element selected from Group VIA of the periodic table and an aqueous solution containing at least one element selected from Group VIII of the periodic table, and then dried. It is easily obtained by doing. Further, the temperature during drying is preferably in the range of 105 to 300 ° C. Subsequent to this drying, it is preferable from the viewpoint of improving the desulfurization effect that the present catalyst is further subjected to sulfiding treatment with a sulfur-containing gas or the like.
• the absorbance of the acidic OH group, the absorbance of the basic OH group, the pore volume and the average pore diameter in the catalyst support were measured as follows.
• Pore volume and average pore diameter It was measured by a mercury intrusion method (mercury contact angle: 150 degrees, surface tension: 480 dyn / cm).
• the pore volume was a pore volume having a pore diameter of 40 mm or more, and the average pore diameter was a pore diameter corresponding to 50% of the pore volume.
• the degree of vacuum was 1.0 ⁇ 10 ⁇ 3 Pa or less, and then cooled to room temperature, and the absorbance was measured.
• the number of integrations is 200 times baseline corrected wavenumber range 3000 ⁇ 4000 cm -1, then corrected with a specific surface area. Absorbance was converted per unit surface area and per unit mass.
• the wave number of the maximum peak position of the absorption spectrum due to the nuclei was in the range of 3670 to 3695 cm ⁇ 1
• the wave number of the maximum peak position of the absorption spectrum due to the basic OH group was in the range of 3760 to 3780 cm ⁇ 1 .
• Example 1 [Preparation of Hydrotreating Catalyst Support (1)] (First Production Method) (Process (a)) A tank with a 100 L steam jacket was charged with 8.78 kg of a sodium aluminate aqueous solution having a concentration of 22% by mass in terms of Al 2 O 3 and diluted with ion-exchanged water to 29.83 kg. Next, 109.6 g of a 26 mass% sodium gluconate aqueous solution was added to this solution and heated to 60 ° C. with stirring to prepare a 5 mass% sodium aluminate aqueous solution in terms of Al 2 O 3 .
• an aluminum sulfate aqueous solution obtained by diluting 13.13 kg of an aluminum sulfate aqueous solution having a concentration of 7% by mass in terms of Al 2 O 3 with 23.64 kg of ion-exchanged water, and 272.7 g of titanium sulfate having a concentration of 33% by mass in terms of TiO 2 concentration.
• An aluminum sulfate / titanium sulfate mixed aqueous solution heated to 60 ° C. was prepared by mixing 1.80 kg of a 5 mass% titanium sulfate aqueous solution in terms of TiO 2 dissolved in 1.53 kg of ion exchange water.
• the hydrotreating catalyst support (1) obtained by the above-described steps was analyzed for the contents of titania (TiO 2 ), boria (B 2 O 3 ), and alumina (Al 2 O 3 ). Moreover, the pore volume and the average pore diameter were measured. These results are shown in Table 1.
• the nitrogen monoxide (NO) adsorption amount was measured by the following method. The results are shown in Table 1.
• Nitric oxide (NO) adsorption amount (measurement method) The hydrotreating catalyst (1) was pulverized to 60 mesh or less, and about 0.2 g was sealed in a quartz measuring cell and filled into a fully automatic catalytic gas adsorption device (Okura Riken Co., Ltd. model R6015). Thereafter, sulfiding treatment was performed at 320 ° C. for 1 hour in a 5 vol% hydrogen sulfide / 95 vol% hydrogen stream.
• NO gas NO concentration: 10% by volume
• NO gas NO concentration: 10% by volume
• the amount of NO gas adsorbed per 1 g of the catalyst was measured. Since NO molecules are adsorbed on the reaction active sites of the active metal on the catalyst, the dispersibility of the active metal can be evaluated by the amount of adsorption.
• Example 2 [Preparation of Hydrotreating Catalyst Support (2)] (First Production Method) In (Step (a)) of Example 1, 872.4 g of a titanium sulfate aqueous solution having a concentration of 5% by mass in terms of TiO 2 was used, and 51.9 g of boric acid was added in (Step (f) and Step (i)).
• a hydrotreating catalyst support (2) was prepared in the same manner as in Example 1 except that. The obtained hydrotreating catalyst support (2) was subjected to composition analysis, and the pore volume, average pore diameter, absorbance of acidic OH groups, and absorbance of basic OH groups were measured. The results are shown in Table 1.
• hydrotreating catalyst (2) was prepared in the same manner as in Example 1 except that the hydrotreating catalyst support (2) was used.
• the obtained hydrotreating catalyst (2) was subjected to composition analysis and measurement of nitrogen monoxide (NO) adsorption and performance evaluation. The results are shown in Table 1.
• Example 3 [Preparation of Hydrotreating Catalyst Support (3)] (First Production Method) In Example 1 (step (a)), 5.24 kg of titanium sulfate aqueous solution having a concentration of 5% by mass in terms of TiO 2 was used, and 231.3 g of boric acid was added in (step (f) and step (i)). A hydrotreating catalyst support (3) was prepared in the same manner as in Example 1 except that. The obtained hydrotreating catalyst support (3) was subjected to composition analysis, and the pore volume, average pore diameter, absorbance of acidic OH groups, and absorbance of basic OH groups were measured. The results are shown in Table 1.
• hydrotreating catalyst (3) was prepared in the same manner as in Example 1, except that the hydrotreating catalyst support (3) was used.
• the obtained hydrotreating catalyst (3) was subjected to composition analysis and measurement of nitrogen monoxide (NO) adsorption and performance evaluation. The results are shown in Table 1.
• Example 4 [Preparation of carrier for hydrotreating catalyst (4)] (first production method) In the process of Example 1 (a), using a concentration of 5 wt% aqueous solution of sodium silicate 1.80g in terms of SiO 2 instead of 5% by weight of aqueous solution of titanium sulfate 1.80kg in terms of TiO 2, while stirring Al 2 A carrier for hydrotreating catalyst (4) was prepared in the same manner as in Example 1 except that it was added to a sodium aluminate aqueous solution having a concentration of 5% by mass in terms of O 3 and heated to 60 ° C. The resulting hydrotreating catalyst support (4) was subjected to composition analysis and measurement of nitrogen monoxide (NO) adsorption and performance evaluation. The results are shown in Table 1.
• NO nitrogen monoxide
• hydrotreating catalyst (4) was prepared in the same manner as in Example 1, except that the hydrotreating catalyst support (4) was used.
• the obtained hydrotreating catalyst (4) was subjected to composition analysis and measurement of nitrogen monoxide (NO) adsorption and performance evaluation. The results are shown in Table 1.
• Example 5 [Preparation of Hydrotreating Catalyst Support (5)] (First Production Method) In Example 1 (step (f) and step (i)), Example 1 was used except that 98.4 g of 61 mass% monoammonium phosphate in terms of P 2 O 5 was used instead of 107.1 g of boric acid. In the same manner as above, a hydrotreating catalyst support (5) was prepared. The obtained hydrotreating catalyst support (5) was subjected to composition analysis, and the pore volume, average pore diameter, absorbance of acidic OH groups, and absorbance of basic OH groups were measured. The results are shown in Table 1.
• hydrotreating catalyst (5) was prepared in the same manner as in Example 1 except that the hydrotreating catalyst support (5) was used.
• the resulting hydrotreating catalyst (5) was subjected to composition analysis and measurement of nitrogen monoxide (NO) adsorption and performance evaluation. The results are shown in Table 1.
• Example 6 [Preparation of Hydrotreating Catalyst Support (6)] (First Production Method) In Example 5 (step (f) and step (i)), instead of 107.1 g of boric acid of 56% by mass in terms of B 2 O 3 , washing in (step (d) and step (i)) was performed.
• a hydrotreating catalyst support (6) was prepared in the same manner as in Example 1 except that 98.4 g of phosphoric acid having a 61% concentration as P 2 O 5 concentration was added to the cake-like slurry.
• the resulting hydrotreating catalyst support (6) was subjected to composition analysis, and the pore volume, average pore diameter, absorbance of acidic OH groups, and absorbance of basic OH groups were measured. The results are shown in Table 1.
• hydrotreating catalyst (6) was prepared in the same manner as in Example 1, except that the hydrotreating catalyst support (6) was used.
• the obtained hydrotreating catalyst (6) was subjected to composition analysis and measurement of nitrogen monoxide (NO) adsorption and performance evaluation. The results are shown in Table 1.
• an aluminum sulfate aqueous solution obtained by diluting 13.13 kg of an aluminum sulfate aqueous solution having a concentration of 7% by mass in terms of Al 2 O 3 with 23.64 kg of ion-exchanged water, and phosphoric acid 147 having a concentration of 61% by mass in terms of P 2 O 5.
• 0.5 g was mixed and an aluminum sulfate / phosphoric acid mixed aqueous solution heated to 60 ° C. was prepared.
• composition for hydrotreating catalyst support (7) obtained by the above steps was subjected to composition analysis, and the pore volume, average pore diameter, absorbance of acidic OH groups, and absorbance of basic OH groups were measured. The results are shown in Table 1.
• hydrotreating catalyst (7) was prepared in the same manner as in Example 1, except that the hydrotreating catalyst support (7) was used.
• the obtained hydrotreating catalyst (7) was subjected to composition analysis and measurement of nitrogen monoxide (NO) adsorption and performance evaluation. The results are shown in Table 1.
• Example 8 Using the hydrotreating catalyst support (1) of Example 1, a hydrotreating catalyst was prepared as follows. (Preparation of hydrotreating catalyst (8)) Add 500 g of ion-exchanged water to a 1 L beaker, add 295.8 g of molybdenum trioxide and 117.4 g of cobalt carbonate, then add 69.3 g of phosphoric acid and 105.6 g of citric acid, and dissolve by stirring at 95 ° C. for 3 hours. An impregnation liquid (2) was prepared. Next, a hydrotreating catalyst (8) was prepared in the same manner as in Example 1 except that the impregnation liquid (2) was used. The obtained hydrotreating catalyst (8) was subjected to composition analysis and measurement of nitrogen monoxide (NO) adsorption and performance evaluation. The results are shown in Table 1.
• NO nitrogen monoxide
• Example 9 Using the hydrotreating catalyst support (1) of Example 1, a hydrotreating catalyst was prepared as follows. (Preparation of hydrotreating catalyst (9)) Add 400 g of ion-exchanged water to a 1 L beaker, add 448.0 g of molybdenum trioxide and 173.3 g of cobalt carbonate, add 91.8 g of phosphoric acid and 156.0 g of citric acid, and stir at 95 ° C. for 3 hours to dissolve. Thus, an impregnation liquid (3) was prepared. Next, a hydrotreating catalyst (9) was prepared in the same manner as in Example 1 except that the impregnation liquid (3) was used. The obtained hydrotreating catalyst (9) was subjected to composition analysis and measurement of nitrogen monoxide (NO) adsorption and performance evaluation. The results are shown in Table 1.
• NO nitrogen monoxide
• hydrotreating catalyst (R1) A hydrotreating catalyst (R1) was prepared in the same manner as in Example 1 except that the hydrotreating catalyst support (R1) was used. The obtained hydrotreating catalyst (R1) was subjected to composition analysis and measurement of nitrogen monoxide (NO) adsorption and performance evaluation. The results are shown in Table 1.
• Example 2 [Preparation of hydrotreating catalyst support (R2)]
• Step (a) 1.90 kg of an aqueous titanium sulfate solution having a concentration of 5% by mass in terms of TiO 2 was used, and 395.8 g of boric acid was added in (Step (f) and Step (i)).
• a hydrotreating catalyst support (R2) was prepared in the same manner as in Example 1 except for the above.
• the resulting hydrotreating catalyst support (R2) was subjected to composition analysis, and the pore volume, average pore diameter, absorbance of acidic OH groups, and absorbance of basic OH groups were measured. The results are shown in Table 1.
• hydrotreating catalyst (R2) A hydrotreating catalyst (R2) was prepared in the same manner as in Example 1 except that the hydrotreating catalyst support (R2) was used. The obtained hydrotreating catalyst (R2) was subjected to composition analysis and measurement of nitrogen monoxide (NO) adsorption and performance evaluation. The results are shown in Table 1.
• Example 3 [Preparation of Hydrotreating Catalyst Support (R3)]
• Step (a) 109.6 kg of a titanium sulfate aqueous solution having a concentration of 5% by mass in terms of TiO 2 was used, and 456.7 g of boric acid was added in (Step (f) and Step (i)).
• a hydrotreating catalyst support (R3) was prepared in the same manner as in Example 1 except that.
• the resulting hydrotreating catalyst support (R3) was subjected to composition analysis, and the pore volume, average pore diameter, absorbance of acidic OH groups, and absorbance of basic OH groups were measured. The results are shown in Table 1.
• hydrotreating catalyst (R3) A hydrotreating catalyst (R3) was prepared in the same manner as in Example 1 except that the hydrotreating catalyst support (R3) was used. The obtained hydrotreating catalyst (R3) was subjected to composition analysis and measurement of nitrogen monoxide (NO) adsorption and performance evaluation. The results are shown in Table 1.
• hydrotreating catalyst (R4) A hydrotreating catalyst (R4) was prepared in the same manner as in Example 1 except that the hydrotreating catalyst support (R4) was used. The obtained hydrotreating catalyst (R4) was subjected to composition analysis and measurement of nitrogen monoxide (NO) adsorption and performance evaluation. The results are shown in Table 1.
• the hydrotreating catalyst using the hydrotreating catalyst support according to the present invention has a predetermined absorbance due to acidic OH groups and basic OH groups on the catalyst support surface. Therefore, it is excellent in desulfurization activity (hydrogenation activity). On the other hand, desulfurization activity is inferior in Comparative Examples 1 to 4 in which the absorbance described above is out of the predetermined range.

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