WO2014013784A1 - 使用済水素化処理用チタニア触媒の再賦活化方法及び再生水素化処理用チタニア触媒 - Google Patents
使用済水素化処理用チタニア触媒の再賦活化方法及び再生水素化処理用チタニア触媒 Download PDFInfo
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- hydrotreating
- saccharide
- reactivation
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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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/04—Gas or vapour treating; Treating by using liquids vaporisable upon contacting spent catalyst
- B01J38/12—Treating with free oxygen-containing gas
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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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/50—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids
- B01J38/52—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids oxygen-containing
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- 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
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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
- 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
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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
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/20—Regeneration or reactivation
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- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
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- 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
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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
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- 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
- B01J27/28—Regeneration or reactivation
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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
- B01J27/28—Regeneration or reactivation
- B01J27/285—Regeneration or reactivation of catalysts comprising compounds of phosphorus
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/26—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24
- B01J31/38—Catalysts comprising hydrides, coordination complexes or organic compounds containing in addition, inorganic metal compounds not provided for in groups B01J31/02 - B01J31/24 of titanium, zirconium or hafnium
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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
- B01J31/00—Catalysts comprising hydrides, coordination complexes or organic compounds
- B01J31/40—Regeneration or reactivation
- B01J31/4015—Regeneration or reactivation of catalysts containing metals
- B01J31/4053—Regeneration or reactivation of catalysts containing metals with recovery of phosphorous catalyst system constituents
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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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/02—Heat treatment
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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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
- B01J38/50—Liquid treating or treating in liquid phase, e.g. dissolved or suspended using organic liquids
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- 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
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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
- B01J38/00—Regeneration or reactivation of catalysts, in general
- B01J38/48—Liquid treating or treating in liquid phase, e.g. dissolved or suspended
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- 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
- C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
- C10G2300/70—Catalyst aspects
- C10G2300/708—Coking aspect, coke content and composition of deposits
Definitions
- This invention is a method for reactivation of a used hydrotreating titania catalyst for reactivating a used hydrotreating titania catalyst that has been used for hydrotreating a hydrocarbon oil and whose catalytic activity has decreased, And a regenerated hydrotreating titania catalyst reactivated by this method.
- SOx sulfur oxides
- NOx nitrogen oxides
- SOF derived from sulfur content in fossil fuels
- Soluble Organic Fraction solvent soluble matter
- hydrocarbon oil such as gasoline, kerosene oil and heavy oil
- desulfurization can remove sulfur content in hydrocarbon oil more efficiently.
- Development of hydrotreating catalysts with excellent activity is also being promoted.
- hydrotreating catalysts for removing sulfur from petroleum fractions include porous alumina carriers, Group VI metals such as molybdenum and tungsten, and metals such as cobalt and nickel.
- a catalyst carrying Group VIII to X metals of the periodic table is generally used, but a hydrodesulfurization catalyst using a porous titania support is known as one having more excellent desulfurization activity.
- titania has disadvantages such as a small specific surface area, poor moldability, and low mechanical strength compared to alumina, and the raw material is expensive and economically disadvantageous compared to alumina. In fact, it is hardly used industrially as a hydrotreating catalyst for the purpose of desulfurization for removing sulfur content in hydrocarbon oil.
- Patent Document 1 an anion or cation is added as a particle growth inhibitor to a hydrous oxide or hydrogel of a titanium hydrous oxide produced by a pH swing method, or a dried product thereof, followed by drying and firing.
- a high-performance hydrodesulfurization catalyst has been obtained that has excellent stability, a large specific surface area, a highly dispersed catalyst metal, improved catalyst activity, and increased mechanical strength.
- Document 2 proposes a technique for producing a catalyst carrier for hydrorefining treatment that is complexed by coprecipitation of aluminum ions and titanium ions
- Patent Document 3 discloses hydroxycarbon of titanium.
- a method for producing an alumina-titania composite catalyst carrier in which an acid salt and / or titanium oxide, hydroxide sol and hydroxycarboxylic acid are added to an aluminum oxide and / or hydroxide, kneaded and calcined is proposed.
- Patent Document 4 titanium is chemically vapor-deposited on the surface of alumina by introducing titanium tetrachloride gas into the alumina carrier.
- a method of apparently changing the pore surface of the alumina carrier to titania has been proposed.
- Patent Document 5 the alumina carrier is impregnated with a solution containing titanium and dried to dry the pore surface of the alumina. Techniques for coating with titanium have also been proposed.
- Non-Patent Document 1 a titania-alumina carrier is obtained by precipitating (coating) titanium hydroxide on the surface of alumina hydrate particles, and then aging, filtering, washing, molding and firing.
- a method is disclosed, and the present inventors also deposit titanium oxide between the isoelectric points of the inorganic oxide and titanium oxide when the titanium oxide is supported on the surface of the inorganic oxide.
- the inorganic oxide and titanium oxide are chemically and microscopically integrated, and have excellent specific surface area and mechanical strength, and are suitable for hydrodesulfurization catalysts.
- a catalyst production technique that can produce a catalyst equivalent in activity to a titania hydrodesulfurization catalyst has been proposed (Patent Document 6).
- Patent Document 7 the catalyst metal on the alumina carrier, phosphoric acid and divalent alcohols having 2 to 10 carbon atoms contained in one molecule, ethers thereof, monosaccharides, disaccharides and A method for producing a hydrotreating catalyst that is impregnated with a catalyst component-containing aqueous solution containing a polysaccharide additive and dried at 200 ° C. or lower is disclosed, and Patent Document 8 discloses an aqueous solution containing a titanium compound in alumina hydrogel.
- a hydrotreating catalyst In the production of a hydrotreating catalyst by supporting a catalyst metal on a support obtained by firing and supporting a catalyst, a diol or alcohol having a molecular weight of 100 or more and a hydroxyl group and / or an ether bond in a catalyst component-containing aqueous solution , Methods for adding water-soluble organic compounds such as ether group-containing water-soluble polymers, saccharides and polysaccharides have been proposed.
- the titanium hydroxide particles are coated on the surface of the catalyst, then molded and dried, and the resulting titania-coated alumina support is impregnated with a catalyst component-containing aqueous solution containing a catalytic metal compound and a saccharide, and dried to titania for hydrotreatment.
- a method for obtaining a catalyst has been proposed (Patent Document 9).
- any of these titania catalysts for hydrotreating using a titania support makes use of the excellent characteristics of the titania support and overcomes its drawbacks to a certain extent.
- the problem of economic disadvantage has not been overcome.
- Patent Document 10 For example, with respect to a hydrotreating catalyst obtained by supporting a catalyst metal on an inorganic oxide support containing alumina and titania, in Patent Document 10, the hydrotreatment of light oil is performed in the first desulfurization step and the second desulfurization step.
- a regenerated catalyst regenerated by a precipitated coke removal reaction under conditions of an air partial pressure of 0.05 to 5 MPa and a temperature of 200 to 800 ° C. is disclosed.
- Patent Document 11 after a calcination treatment at 300 ° C. for 1 hour in a nitrogen atmosphere, a calcination treatment at 450 ° C. for 3 hours in a mixed gas atmosphere of 50% nitrogen gas and 50% air is performed to regenerate the used catalyst. It is described to do.
- Patent Documents disclose a hydroprocessing catalyst obtained by loading a catalyst metal such as molybdenum, cobalt, nickel, or phosphorus on an alumina carrier containing organic additives such as diethylene glycol, citric acid, and polyethylene glycol in the catalyst.
- a stripping process is performed at 100 to 370 ° C. in the presence of an oxygen-containing gas, and then a regeneration process is performed at 300 to 500 ° C. in the presence of an oxygen-containing gas.
- regeneration treatment is performed at 300 to 650 ° C. in the presence of an oxygen-containing gas, followed by “acid and organic additives such as citric acid and polyethylene glycol, or phosphoric acid and polyethylene glycol”. And activating the used catalyst by impregnation with a solution containing That.
- the present inventors have used a used hydroprocessing titania catalyst that has been used for hydrotreating hydrocarbon oils and has a reduced catalytic activity to a catalytic activity comparable to that of a fresh titania catalyst before use.
- Various studies were made on reactivation and use as a titania catalyst for regenerating hydroprocessing.
- the present inventors further impregnate the dried titania catalyst after the coke removal treatment with a “solution containing an acid and an organic additive” according to the activation method described in Patent Document 13, and dry the catalyst.
- the catalyst activity (desulfurization activity) of the obtained regenerated titania catalyst remained below 65% of the fresh titania catalyst before use. It has been difficult to reactivate to the extent that it can be reused. Although the cause of such a result is not necessarily clear, the present inventors consider as follows.
- the difference between the above titania carrier and alumina carrier is considered as follows. That is, in the case of alumina, the zeta potential hardly changes in the weak acid region of pH 3-7. Therefore, in an alumina catalyst, even if a weak acid is added as an activator for regeneration, it is not affected by the interaction between the support and the catalyst metal molybdenum. On the other hand, in the case of titania, the zeta potential changes greatly from the minus side to the plus side in the corresponding pH range. Therefore, in the titania catalyst, the interaction between the support and the anionic molybdenum oxide is caused by the addition of an acid. Is thought to strengthen.
- the present inventors surprisingly include saccharides in the carbonaceous removal catalyst obtained by the coke removal treatment.
- the catalytic activity (desulfurization activity) of the regenerated titania catalyst is comparable to the freshly prepared fresh titania catalyst.
- the present invention has been completed.
- an object of the present invention is to provide a titania catalyst for hydrotreating obtained by loading a catalyst component on a titania support, which is used for hydrotreating hydrocarbon oil and has a reduced catalyst activity.
- Another object of the present invention is to provide a reactivation method of a used titania catalyst for hydroprocessing that can be increased to a level comparable to that of a freshly prepared titania catalyst before use.
- Another object of the present invention is a regenerated hydrotreating titania regenerated by the above-described method for reactivation of a used hydrotreating titania catalyst and having a catalytic activity comparable to that of a fresh titania catalyst before use. It is to provide a catalyst.
- the present invention relates to a titania catalyst for hydrotreating obtained by loading a catalyst component on a titania carrier, and reactivating a used catalyst that has been used for hydrotreating hydrocarbon oil and has reduced catalytic activity.
- a coke removal step in which the spent catalyst is heated in an oxygen-containing gas atmosphere to remove carbonaceous components on the catalyst surface, and the carbonaceous removal catalyst obtained in the coke removal step has a saccharide
- the present invention is a regenerated hydrotreating titania catalyst obtained by the above-described method for reactivation of a spent hydrotreating titania catalyst.
- the hydrotreating catalyst to be reactivated is a titania catalyst for hydrotreating obtained by loading a catalyst component on a titania carrier, and used for hydrotreating hydrocarbon oil. This is a titania catalyst after use with reduced catalytic activity.
- the titania carrier a titania carrier having a higher specific surface area and higher thermal stability than conventional titania is preferable, and examples thereof include known ones such as titania as disclosed in Patent Document 1. From the viewpoint of catalyst strength and catalyst production cost, it is not just a mixture of alumina and titania, but a titania-coated alumina carrier having a titania coating layer on the surface of alumina as shown in Patent Documents 4, 6, and 9. Is more preferable.
- the catalyst component supported on the titania carrier is usually at least one group VI metal compound in the periodic table, at least one group VIII to X metal compound in the periodic table, and at least one phosphorus compound. Includes seeds.
- the group VI metal of the periodic table preferably includes molybdenum and tungsten, and molybdenum is particularly preferable.
- preferable molybdenum compounds include molybdenum trioxide, molybdic acid, ammonium molybdate, and ammonium paramolybdate. Is mentioned.
- examples of the metals in Group VIII to X of the periodic table include cobalt and nickel.
- Preferred nickel compounds include nickel nitrate, nickel sulfate, nickel acetate, nickel carbonate, nickel chloride, nickel hydroxide, basic nickel carbonate.
- preferred cobalt compounds include cobalt nitrate, cobalt sulfate, cobalt acetate, basic cobalt carbonate, cobalt carbonate, cobalt chloride, cobalt hydroxide, and the like. These cobalt compounds and nickel compounds are Any one of them may be used alone, or two or more of them may be used in combination.
- preferable phosphorus compounds include phosphorus pentoxide, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, disodium hydrogen phosphate, sodium dihydrogen phosphate, orthophosphoric acid and the like.
- a freshly prepared titania catalyst for hydroprocessing before use which contains a conventionally known organic additive that contributes to catalytic activity in addition to the above catalyst components, is added to the above titania support. It may be obtained by impregnating the component-containing solution and drying, and examples of the organic additive used for this purpose include organic acids, aliphatic dialcohols, ethers and polyethers, saccharides, Examples thereof include nitrogen-containing compounds.
- the used titania catalyst that has been used for hydrotreating hydrocarbon oil and has reduced catalytic activity is, for example, a sulfur content in petroleum fractions (hydrocarbon oil) such as gasoline, kerosene oil, and heavy oil. It is used for hydrotreating (desulfurization treatment) for the purpose of removal of carbon and its catalytic activity accumulates on the catalyst with the course of use, and falls to about 60% or less of the initial catalytic activity. It means that the sulfur concentration after hydrotreating (for example, 10 ppm or less in the case of light oil) cannot be achieved, and used titania catalyst for hydrotreating recovered from this hydrotreating step.
- hydrocarbon oil such as gasoline, kerosene oil, and heavy oil.
- [Coke removal process] when reactivating the above-described spent hydrotreating titania catalyst, first, in the coke removal step, 350 ° C. or more and 600 ° C. or less, preferably 400 ° C. or more and 550 ° C. or less in an oxygen-containing gas atmosphere.
- the coke removal treatment is performed by heating at a temperature of 5%, and the carbonaceous components present on the surface of the used catalyst and causing the decrease in the catalyst activity are burned and removed.
- the carbonaceous component may be calcined under a condition that the content is 3% by weight or less, preferably 2% by weight or less.
- the oxygen-containing gas used here may be any oxygen-containing gas as long as it contains oxygen and can burn and remove the carbonaceous component on the surface of the used catalyst. Usually, air, oxygen-containing nitrogen gas, or the like is used. Further, the heating temperature varies depending on the type of titania support to be used, but if it is lower than 350 ° C., it becomes difficult to completely burn and remove the carbonaceous component on the surface of the used catalyst. If it is higher, problems such as alteration of the support and aggregation of the supported catalyst metal occur.
- the carbonaceous removal catalyst obtained in the coke removal step is then impregnated with a saccharide-containing solution in the impregnation step.
- the saccharides used for this purpose are not particularly limited.
- monosaccharide trioses glycosaldehyde, dihydroxyacetone, glycerin
- tetroses erythrose, threose, erythrulose, erythritol, etc.
- pentoses Rosicose, fructose, sorbose, tagose, allose, altrose, glucose, mannose, gulose, idose, galactose, talose, fucose, Fucose, rhamnose, sorbi
- the saccharide-containing solution used in this impregnation step is preferably glucose, fructose, erythritol, xylose, xylitol, sorbitol, mannitol, invert sugar, maltose, trehalose, maltitol, isomerized sugar, and raffinose from the viewpoint of economy. It may be a solution such as water or alcohol containing one or more saccharides selected from the group consisting of:
- the saccharide concentration of the saccharide-containing solution used in this impregnation step is not particularly limited, but at a low concentration, only an amount corresponding to the pore volume of the carrier can be impregnated.
- concentration is high, the viscosity of the solution increases and the solution cannot sufficiently penetrate into the catalyst pores. Therefore, it is necessary to adjust the concentration within a range suitable for the saccharide.
- it is 5% by mass or more and 60% by mass or less, preferably 10% by mass or more and 50% by mass or less, and if it is thinner than 2% by mass, there is a problem that a desired amount of impregnation cannot be achieved. If the concentration is higher than%, there may be a problem that sugar does not completely dissolve.
- the carbonaceous removal catalyst is impregnated with the saccharide-containing solution in this impregnation step, and the amount of saccharide used to be dried and supported on the carbonaceous removal catalyst in the next drying step is about 100 parts by mass of the carbonaceous removal catalyst. On the other hand, it is usually 2 to 30 parts by mass, preferably 5 to 25 parts by mass. If the amount of saccharide used is less than 2 parts by mass, the effect of saccharide addition does not remarkably appear. On the contrary, even if the amount exceeds 30 parts by mass, the effect of saccharide addition reaches a peak.
- the saccharide is allowed to stand in that state for a predetermined time in order to uniformly and stably carry the saccharide on the carbonaceous removal catalyst.
- the aging time is preferably in the range of 10 minutes to 24 hours.
- the catalyst component added to the saccharide-containing solution should be the same catalyst component as the catalyst component supported on the titania carrier in the hydrotreating titania catalyst before use, that is, in the periodic table.
- the catalyst component may be a catalyst component including at least one group VI metal compound, at least one group VIII-X metal compound of the periodic table, and at least one phosphorus compound, and more preferably used.
- the same compounds may be used for the Group VI metal compound, Group VIII to X metal compound of the periodic table, and the phosphorus compound used in the previous hydrotreating titania catalyst.
- the addition amount of the catalyst component added to the saccharide-containing solution should be an amount that can compensate for the loss of the catalyst component lost by the coke removal treatment during use and / or reactivation of the catalyst.
- the loss amount of the catalyst component is empirically about 5% by mass or less, and if it is added more than necessary, there is a possibility that association with the original catalyst component may occur and the catalytic activity may be lowered.
- the desired catalytic activity for example, 70% of the titania catalyst for hydrotreating before use
- the periodicity in the catalyst component is obtained after reactivation.
- the total amount of the Group VI metal compound, Group VIII to X metal compound of the periodic table, and the phosphorus compound is 5% by mass or less of the catalyst component of the regenerated hydrotreating titania catalyst after reactivation in terms of oxide. It is good to be.
- the saccharide impregnated catalyst obtained by impregnating the saccharide-containing solution in the impregnation step is then dried to stably support the saccharide on the carbonaceous removal catalyst, and the activated titania catalyst for regenerated hydroprocessing is activated.
- the drying temperature is 100 ° C. or higher and 400 ° C. or lower, preferably 110 ° C. or higher and 300 ° C. or lower, and 0.5 hour or longer and 24 hours or shorter, preferably 1 hour or longer and 12 hours or shorter.
- the drying time should be within a range.
- drying temperature varies depending on the type of titania carrier used, it can be easily imagined that when the temperature is lower than 100 ° C., moisture remains and causes various problems when subjected to the reaction. On the other hand, when the temperature is higher than 400 ° C., a problem that the saccharide is carbonized occurs.
- the regenerated hydrotreating titania catalyst obtained by the method of the present invention has a catalytic activity (desulfurization activity) that is comparable to that of a new hydrotreating titania catalyst before use, specifically, a new before use.
- a catalytic activity of the titania catalyst for hydrotreating is 100, it recovers to a value exceeding 70%, preferably to a value exceeding 75%.
- the hydrotreating is usually performed again as it is. Can be used.
- the use method of the titania catalyst for regenerating hydrotreating of the present invention will be described as follows by taking hydrocarbon oil hydrotreating, particularly desulfurization treatment as an example.
- the preliminary sulfiding agent hydrogen sulfide, carbon disulfide, thiophene, dimethyl disulfide, or a hydrocarbon oil containing them is used.
- the desulfurization treatment is performed after the preliminary desulfurization.
- the treatment conditions for the desulfurization treatment vary depending on the type and purpose of the feedstock, but generally the reaction temperature is in the range of 250 to 450 ° C. and the hydrogen partial pressure is 1 It is preferable to be in the range of ⁇ 15 MPa.
- reaction format in this desulfurization process is not specifically limited, A fixed bed, a moving bed, a boiling bed, a suspension bed, etc. are mentioned, Any may be employ
- the reaction conditions when a fixed bed is employed the liquid hourly space velocity (LHSV) is preferably in the range of 0.1 to 5 hr ⁇ 1 and the hydrogen / feed oil volume ratio is preferably in the range of 50 to 500 Nm 3 / kl.
- hydrocarbon oils that can be treated using the titania catalyst for regenerating hydrotreating of the present invention include gasoline, kerosene, light gas oil, heavy gas oil, cracked gas oil, etc. Oil sand oil, tar sand oil, etc.
- a used hydroprocessing titania catalyst used for hydrotreating hydrocarbon oil and having a reduced catalytic activity is reactivated to a level comparable to that of a fresh titania catalyst before use. Since the catalytic activity can be recovered, the obtained regenerative hydrotreating titania catalyst can be used in the same manner as a fresh titania catalyst almost in the same manner. For this reason, according to the present invention, while taking advantage of the excellent characteristics of the titania carrier, it is possible to overcome the disadvantage of "economic disadvantage", which has been a big problem from an industrial point of view. It is extremely useful industrially.
- the pore distribution and pore volume of the catalyst and the carrier were measured by a mercury intrusion method using Shimadzu Autopore IV9520 type and pressurizing up to a measurement pressure of 414 MPa.
- the hydrodesulfurization test of light oil for measuring the desulfurization activity of the hydrotreating catalyst was performed as follows. Using a high-pressure fixed-bed flow reactor, 15 ml of catalyst was charged, under conditions of reaction pressure: 5 MPa, reaction temperature: 340 ° C., liquid space velocity 1.5 h ⁇ 1 , and hydrogen / raw material volume ratio: 250 Nl / l. Carried out.
- the hydrotreating catalyst used in the test is one that has been subjected to sulfidation treatment (preliminary sulfidation) using light oil with dimethyl disulfide added in advance and the sulfur concentration adjusted to 2.5% (mass basis). Using.
- distillation properties are the initial distillation temperature of 228 ° C. 50% distillation temperature 293 ° C and 90% distillation temperature 347 ° C.
- the desulfurization activity of the hydrotreating catalyst was determined by taking the desulfurization reaction as the first order reaction, obtaining the desulfurization reaction rate constant, and calculating the average value of the desulfurization reaction rate constant during the reaction time of 100 to 144 hours.
- the average values of the desulfurization reaction rate constants of the hydrotreating titania catalyst HBT-1 of No. 1 and the alumina catalyst ALC-1 for hydrotreating of Reference Example 2 were set to 100, respectively.
- the relative desulfurization activity relative to the catalyst for use was determined and expressed as “relative desulfurization activity”.
- Hydrochloric acid 733 g and water 13 g were added to titanium tetrachloride solution 1520 g having a mass of 7% by mass and a Cl concentration of 32.6% by mass to prepare E solutions in the total amount necessary for the operations described below.
- the titania-coated alumina hydrate particles were produced by adding in a range of 0.0 ⁇ 0.1.
- the titania coating amount in the obtained titania-coated alumina hydrate particles is 31%.
- the ammonia ions and chlorine ions coexisting with the titania-coated alumina hydrate particles thus obtained were washed and removed with water and filtered to adjust the moisture content to be moldable, and by extrusion molding, the diameter was 1.2 mm. After being molded into a cylindrical shape (molding step), it was dried at 120 ° C. for 16 hours, and further fired at 500 ° C. for 3 hours (first drying step) to obtain a titania-coated alumina carrier.
- a component aqueous solution was obtained.
- 4.3 g of sorbitol was further dissolved in 27.6 g of the obtained catalyst component aqueous solution to obtain a catalyst component-containing aqueous solution.
- the specific surface area, pore volume, and pore sharpness degree of the obtained hydrotreating titania catalyst were 232 m 2 / g, 0.36 ml / g, and 70.2%, respectively.
- the hydrodesulfurization test of light oil using this catalyst was carried out under the above reaction conditions, and the average value of the desulfurization reaction rate constant was set to 100, and the regeneration obtained in the following Examples 1 to 5 and Comparative Examples 1 to 3 were used. This was used as a standard for evaluating the catalytic activity (relative desulfurization activity) of a titania catalyst for hydroprocessing (hereinafter referred to as “regenerated catalyst”).
- Example 1 The used hydrotreating titania catalyst HBT-1 recovered for about 1 year in a light oil hydrodesulfurization unit was washed with toluene solvent and then dried at 120 ° C for 10 hours in an air atmosphere. Was removed. The catalyst at this point contained 14.7 wt% carbon and 8.5 wt% sulfur.
- Example 2 The catalyst RHBT-1 after 30 g of coke removal treatment was impregnated with an aqueous solution containing 22.5 wt% glucose, and the catalyst was impregnated with a glucose content of 10 wt%. Drying for a period of time gave a regenerated catalyst RHBT-3.
- Example 3 The catalyst RHBT-1 after 30 g of coke removal treatment was impregnated with an aqueous solution containing glucose at a rate of 12.0 wt%, and the catalyst was impregnated so that the glucose content was 5 wt%. Drying for a period of time gave a regenerated catalyst RHBT-4.
- Example 4 An aqueous solution containing sucrose at a ratio of 21.9 wt% was impregnated into 30 g of the catalyst RHBT-1 after the coke removal treatment, and the catalyst was impregnated so that the sucrose content was 10 wt%. Drying for a period of time gave a regenerated catalyst RHBT-5.
- Example 5 An aqueous solution containing 22.4 wt% of maltitol was impregnated into the catalyst RHBT-1 after 30 g of coke removal treatment, and the catalyst was impregnated so that the maltitol content was 10 wt%. For 3 hours to obtain a regenerated catalyst RHBT-6.
- Example 6 The catalyst RHBT-1 after 30 g of coke removal treatment contains sorbitol in a proportion of 22.4 wt%, and the catalyst component is 4.5 g of molybdenum oxide in terms of MoO 3 and 0.8 g of cobalt carbonate in terms of CoO. And an aqueous solution containing 0.7 g of phosphoric acid in terms of P 2 O 5 , the catalyst was impregnated so that the content of sorbitol was 10 wt%, dried at 120 ° C. for 3 hours, and regenerated catalyst RHBT-9 was obtained.
- Comparative Example 1 The regenerated catalyst of Comparative Example 1 was RHBT-1 of the catalyst after the coke removal treatment obtained in Example 1 above.
- the specific surface area was 346 m 2 / g
- the pore volume was 0.5 ml / g
- the degree of pore sharpness was 65.9%.
- alumina carrier obtained above was impregnated with the above aqueous solution containing the catalyst component, and further dried at 120 ° C. for 12 hours to obtain a titania catalyst ALC-1 for hydrotreatment.
- the specific surface area, pore volume, and pore sharpness degree of the resulting hydrotreating alumina catalyst were 195 m 2 / g, 0.35 ml / g, and 62.4%, respectively.
- the hydrodesulfurization test of light oil using this catalyst was carried out under the above reaction conditions, the average value of the desulfurization reaction rate constant was set to 100, and the catalytic activity (relative to the relative catalyst obtained in Comparative Examples 4 to 6 below) The desulfurization activity) was evaluated.
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Abstract
Description
例えば、特許文献1においては、pHスイング法により製造したチタンの含水酸化物のヒドロゾル又はヒドロゲル若しくはそれらの乾燥物に、粒子成長抑制剤としてアニオン、カチオンを添加し、乾燥、焼成することにより、熱安定性に優れ比表面積が大きく、触媒金属が高分散され触媒の活性も向上させながら機械的強度も大きくした高性能な水素化脱硫触媒を得ている。
本発明においては、上記の使用済水素化処理用チタニア触媒を再賦活化するに際して、先ず、コーク除去工程において、酸素含有ガス雰囲気下に350℃以上600℃以下、好ましくは400℃以上550℃以下の温度で加熱するコーク除去処理を行い、この使用済触媒の表面に存在して触媒活性低下の原因になっている炭素質成分を燃焼させて除去する。一般に、炭素質成分の含有量は、3重量%以下、好ましくは2重量%以下となる条件で焼成処理すれば良い。この際に用いられる酸素含有ガスとしては、それが酸素を含んでいて使用済触媒表面の炭素質成分を燃焼し除去できるものであればよく、通常、空気、酸素含有窒素ガス等が用いられる。また、加熱温度については、使用されるチタニア担体の種類によっても異なるが、350℃より低いと使用済触媒表面の炭素質成分を完全に燃焼させて除去することが難しくなり、反対に、600℃より高くなると担体の変質や担持されている触媒金属の凝集を引き起こすといった問題が発生する。
このコーク除去工程で得られた炭素質除去触媒については、次に、含浸工程で糖類含有溶液が含浸される。この目的で用いられる糖類としては、特に制限されるものではなく、例えば、単糖類のトリオース類(グリセルアルデヒド、ジヒドロキシアセトン、グリセリン)、テトロース類(エリトロース、トレオース、エリトルロース、エリスリトール等)、ペントース類(リブロース、キシルロース、リボース、アラビノース、キシロース、キシリトール、リキソース、デオキシリボース等)、ヘキソース類(プシコース、フルクトース、ソルボース、タガトース、アロース、アルトロース、グルコース、マンノース、グロース、イドース、ガラクトース、タロース、フコース、フクロース、ラムノース、ソルビトール、マンニトール、ズルシトール、ガラクチトール、グルコサミン、ガラクトサミン、イノシトール、転化糖等)、ヘプトース類(セドヘプツロース等)、二糖類のスクロース、ラクトース、マルトース、トレハロース、マルチトール、ツラノース、セロビオース、ゲンチオビオース、イソマルトース、コージビオース、ラミナリビオース、メリビオース、ニゲロース、ソフォロース、三糖類のラフィノース、メレジトース、マルトトリオース、四糖類のアカルボース、スタキオース、オリゴ糖類のフラクトオリゴ糖、ガラクトオリゴ糖、マンナンオリゴ糖、多糖類のグリコーゲン、デンプン、セルロース、デキストリン、グルカン、フルクタン、グアーガム、N-アセチルグルコサミン、異性化糖等が挙げられる。
上記含浸工程で糖類含有溶液を含浸させて得られた糖類含浸触媒については、次に、乾燥させて糖類を炭素質除去触媒に安定的に担持させ、賦活化された再生水素化処理用チタニア触媒を得るが、この乾燥工程での乾燥条件については、100℃以上400℃以下、好ましくは110℃以上300℃以下の乾燥温度及び0.5時間以上24時間以下、好ましくは1時間以上12時間以下の乾燥時間の範囲であるのがよい。乾燥温度については、使用されるチタニア担体の種類によっても異なるが、100℃より低いと水分が残存し反応に供した時、諸々の問題を引き起こすことが容易に想像できる。また、反対に、400℃より高くなると、糖類が炭化するという問題が発生する。
各種物性の測定に際しては、予め測定対象物を500℃で3時間の条件で焼成処理した後に、分析に供した。
触媒や担体の細孔分布及び細孔容積は、島津製作所製オートポアIV9520型を使用し、測定圧力414MPa迄加圧する水銀圧入法により測定した。
「細孔シャープネス度」とは、細孔径の均一性を規定する数値である。すなわち、細孔シャープネス度が100%に近づくほど触媒や担体の細孔径が均一で揃っていることを意味する。すなわち、細孔容積の50%における細孔径(メディアン径)を求め、次にメディアン径の対数値の±5%の細孔径範囲内に存在する部分細孔容積(PVM)を求め、その部分細孔容積(PVM)と細孔容積(PVT)から、以下の式により細孔シャープネス度を求めるものである。具体的には、細孔シャープネス度は、水銀圧入法により測定された累積細孔分布曲線から下式により計算することができる。
細孔シャープネス度(%)=(PVM/PVT)×100
水素化処理触媒の脱硫活性を測定するための軽油の水素化脱硫試験は、以下のようにして行った。
高圧の固定床流通式反応装置を用い、触媒を15ml充填し、反応圧力:5MPa、反応温度:340℃、液空間速度1.5h-1、及び水素/原料容積比:250Nl/lの条件で実施した。試験に供した水素化処理用触媒は、予め、全てジメチルジスルフィドを添加し、硫黄濃度を2.5%(質量基準)に調整した軽油を用いて、硫化処理(予備硫化)を施したものを用いた。水素化脱硫試験に供した中東系直留軽油の性状は、比重(15/4℃):0.849、硫黄分:1.21質量%、窒素分:96ppm、蒸留性状は初留温度228℃、50%留出温度293℃及び90%留出温度347℃である。
<原料液の調製>
塩化アルミニウム六水和物970gに水1030gの割合で加えたA液、28%-アンモニア水1000gに水1000gの割合で加えたB液、Ti濃度が16.6質量%、Cl濃度が32.3質量%である四塩化チタン溶液198gに水を加えて1.8リットル(L)としたC液、及び14%アンモニア水231gに水を加えて1.8LとしたD液、Ti濃度が16.7質量%、Cl濃度が32.6質量%である四塩化チタン溶液1520gに塩酸733gと水13gを加えE液をそれぞれ以下に説明する操作に必要な全量調製した。
<アルミナ水和物粒子の製造>
(a) 19Lのホーロー容器に水を14L入れ、攪拌しながら80℃に加熱した。当該ホーロー容器にA液を850g加え5分間保持した。この時の液(以下、「合成溶液」という。)のpHは2.5であった。次に、このホーロー容器に、合成溶液のpHが7.5になる量のB液を加え、5分間保持した(pHスイング回数1回目)。
上で得られたアルミナ水和物粒子を酸化物基準で122g採取し、水を加えながらミキサーで良く撹拌し、8Lの分散液とした。この分散液を60℃に保ちながら、C液を加えpHを5.0に調整し、続いてC液及びD液各1.8Lを約2時間かけて同時に、且つ、連続的にpHを5.0±0.1の範囲に保つように添加し、チタニアコーティングアルミナ水和物粒子を製造した。得られたチタニアコーティングアルミナ水和物粒子におけるチタニアのコーティング量は31%である。
結果は、比表面積が400m2/g、細孔容積が0.57ml/g、及び細孔シャープネス度が76.5%であり、また、チタニアのアナターゼ結晶は検出されなかった。
酸化モリブデン34.5g、CoO換算で7.7g相当の炭酸コバルト、及び85%リン酸5.0gを水に添加して、撹拌しながら加温して溶解し、全量を100.0gにした触媒成分水溶液を得た。得られた触媒成分水溶液27.6gに更にソルビトール4.3gを溶解させ、触媒成分含有水溶液を得た。
本触媒を用いた軽油の水素化脱硫試験を前述の反応条件で実施し、その脱硫反応速度定数の平均値を100とし、以下の実施例1~5及び比較例1~3で得られた再生水素化処理用チタニア触媒(以下、「再生触媒」という。)の触媒活性(相対脱硫活性)を評価する基準とした。
〔実施例1〕
軽油の水素化脱硫装置で、約1年間運転し回収された使用済みの水素化処理用チタニア触媒HBT-1をトルエン溶媒で油分を洗浄後、空気雰囲気下に120℃で10時間乾燥して溶媒を除去した。この時点での触媒中には、炭素分が14.7wt%、硫黄分が8.5wt%含有されていた。
30gのコーク除去処理後の触媒RHBT-1に、グルコースを22.5wt%の割合で含む水溶液を用い、この触媒に対してグルコースの含有量が10wt%になるように含浸し、120℃で3時間乾燥し、再生触媒RHBT-3を得た。
30gのコーク除去処理後の触媒RHBT-1に、グルコースを12.0wt%の割合で含む水溶液を用い、この触媒に対してグルコースの含有量が5wt%になるように含浸し、120℃で3時間乾燥し、再生触媒RHBT-4を得た。
30gのコーク除去処理後の触媒RHBT-1に、スクロースを21.9wt%の割合で含む水溶液を用い、この触媒に対してスクロースの含有量が10wt%になるように含浸し、120℃で3時間乾燥し、再生触媒RHBT-5を得た。
30gのコーク除去処理後の触媒RHBT-1に、マルチトールを22.4wt%の割合で含む水溶液を用い、この触媒に対してマルチトールの含有量が10wt%になるように含浸し、120℃で3時間乾燥し、再生触媒RHBT-6を得た。
30gのコーク除去処理後の触媒RHBT-1に、ソルビトールを22.4wt%の割合で含み、また、触媒成分としてMoO3算で4.5gの酸化モリブデンを、CoO換算で0.8gの炭酸コバルトを、及びP2O5換算で0.7gのリン酸を含む水溶液を用い、この触媒に対してソルビトールの含有量が10wt%になるように含浸し、120℃で3時間乾燥し、再生触媒RHBT-9を得た。
上記の実施例1で得られたコーク除去処理後の触媒のRHBT-1を比較例1の再生触媒とした。
コーク除去処理後の触媒RHBT-1に実施例1と同様にしてクエン酸5wt%+ポリエチレングリコール5wt%になるように含浸し、120℃で3時間乾燥し、再生触媒RHBT-7を得た。
コーク除去処理後の触媒RHBT-1に実施例1と同様にしてクエン酸5wt%+グルコース5wt%になるように含浸し、120℃で3時間乾燥し、再生触媒RHBT-8を得た。
上記実施例1~6及び比較例1~3で得た再生触媒の水素化処理触媒の脱硫活性を測定するため、前述の〔軽油の脱硫試験〕に記載した軽油の水素化脱硫試験を実施し、その相対脱硫活性を表1にまとめて示した。
参考例1の<アルミナ水和物粒子の製造>で得たアルミナ水和物粒子と共存するアンモニアイオン及び塩素イオンを水で洗浄・除去し、ろ過することで成形可能な水分率に調整し、押出し成型により直径1.2mmの円柱状に成型(成形工程)後、120℃で16時間乾燥し、更に500℃で3時間焼成を行い(第1乾燥工程)、アルミナ担体を得た。
酸化モリブデン34.5g、CoO換算で7.7g相当の炭酸コバルト、及び85%リン酸5.0gを水に添加して、撹拌しながら加温して溶解し、全量を100gにした触媒成分水溶液を得た。得られた触媒成分水溶液27.6gに更にソルビトール4.3gを溶解させ、触媒成分含有水溶液を得た。
得られた水素化処理用アルミナ触媒の比表面積、細孔容積、細孔シャープネス度はそれぞれ、195m2/g、0.35ml/g、62.4%であった。
本触媒を用いた軽油の水素化脱硫試験を前述の反応条件で実施し、その脱硫反応速度定数の平均値を100とし、以下の比較例4~6で得られた再生触媒の触媒活性(相対脱硫活性)を評価する基準とした。
〔比較例4〕
軽油の水素化脱硫装置で、約1年間運転し回収された使用済みの水素化処理用チタニア触媒ALC-1をトルエン溶媒で油分を洗浄後、空気雰囲気下に120℃で10時間乾燥して溶媒を除去した。この時点での触媒中には、炭素分が16.7wt%、硫黄分が8.2wt%含有されていた。
30gの再生触媒RALC-1に、ソルビトールを22.1wt%の割合で含む水溶液を用、この触媒に対してソルビトールの含有量が10wt%になるように含浸し、120℃で3時間乾燥し、再生触媒RALC-2を得た。
30gの再生触媒RALC-1に、グルコースを22.5wt%の割合で含む水溶液を用い、この触媒に対してグルコースの含有量が10wt%になるように含浸し、120℃で3時間乾燥し、再生触媒RALC-3を得た。
表2に、上記比較例4~6で得た再生触媒の水素化処理触媒の脱硫活性を測定するため、前述の〔軽油の脱硫試験〕に記載した軽油の水素化脱硫試験を実施し、その相対脱硫活性をまとめて示した。
Claims (9)
- チタニア担体に触媒成分を担持させて得られた水素化処理用チタニア触媒であって、炭化水素油の水素化処理に用いられて触媒活性が低下した使用済触媒を再賦活化するための方法であり、
前記使用済触媒を酸素含有ガス雰囲気下に加熱して触媒表面の炭素質成分を除去するコーク除去工程と、
前記コーク除去工程で得られた炭素質除去触媒に糖類含有溶液を含浸させる含浸工程と、
前記含浸工程で得られた糖類含浸触媒を乾燥させて糖類が担持された触媒を得る乾燥工程とを有することを特徴とする使用済水素化処理用チタニア触媒の再賦活化方法。 - 前記チタニア担体が、アルミナの表面にチタニアコーティング層を有するチタニアコーティングアルミナ担体である請求項1に記載の使用済水素化処理用チタニア触媒の再賦活化方法。
- 前記触媒成分が、周期律表第VI族金属化合物の少なくとも1種、周期律表第VIII~X族金属化合物の少なくとも1種、及びリン化合物の少なくとも1種を含む請求項1又は2に記載の使用済水素化処理用チタニア触媒の再賦活化方法。
- 前記含浸工程で用いられる糖類含有溶液が、グルコース、フルクトース、エリスリトール、キシロース、キシリトール、ソルビトール、マンニトール、転化糖、マルトース、トレハロース、マルチトール、異性化糖、及びラフィノースからなる群より選ばれた1種又は2種以上の糖類を含む溶液である請求項1~3のいずれかに記載の使用済水素化処理用チタニア触媒の再賦活化方法。
- 前記含浸工程で用いられる糖類含有溶液が、糖類に加えて、周期律表第VI族金属化合物の少なくとも1種、周期律表第VIII~X族金属化合物の少なくとも1種、及びリン化合物の少なくとも1種からなる触媒成分を含む溶液である請求項1~4のいずれかに記載の使用済水素化処理用チタニア触媒の再賦活化方法。
- 前記糖類含有溶液に含まれる触媒成分が、チタニア担体に担持させた水素化処理用チタニア触媒の触媒成分と同じ触媒成分である請求項5に記載の使用済水素化処理用チタニア触媒の再賦活化方法。
- 前記糖類含有溶液に含まれる触媒成分中の周期律表第VI族金属化合物、周期律表第VIII~X族金属化合物、及びリン化合物の合計量が、酸化物換算で再賦活化後の再生水素化処理用チタニア触媒の触媒成分の5質量%以下である請求項5又は6に記載の使用済水素化処理用チタニア触媒の再賦活化方法。
- 前記コーク除去工程で用いられる酸素含有ガスが空気である請求項1~[4]7のいずれかに記載の使用済水素化処理用チタニア触媒の再賦活化方法。
- 請求項1~8に記載のいずれかの方法で再賦活化された再生水素化処理用チタニア触媒。
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BR112020000812A2 (pt) | 2017-07-21 | 2020-07-14 | Albemarle Europe Srl | catalisador de hidrotratamento com um veículo contendo titânio e aditivo orgânico |
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MX2017010801A (es) | 2017-08-23 | 2019-03-07 | Mexicano Inst Petrol | Proceso no destructivo para remover metales, iones metalicos y oxidos metalicos de materiales a base de alumina. |
CN109926081A (zh) * | 2017-12-15 | 2019-06-25 | 中国科学院大连化学物理研究所 | 一种用于1,2-二氯乙烷裂解制氯乙烯的催化剂、制备和再生方法 |
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