Classifications

• • 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
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/061—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof containing metallic elements added to the zeolite
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  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C4/00—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms
  • C07C4/02—Preparation of hydrocarbons from hydrocarbons containing a larger number of carbon atoms by cracking a single hydrocarbon or a mixture of individually defined hydrocarbons or a normally gaseous hydrocarbon fraction
  • C07C4/06—Catalytic processes
• • 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
  • B01J29/00—Catalysts comprising molecular sieves
  • B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
  • B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • B01J29/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively
  • B01J29/405—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11, as exemplified by patent documents US3702886, GB1334243 and US3709979, respectively containing rare earth elements, titanium, zirconium, hafnium, zinc, cadmium, mercury, gallium, indium, thallium, tin or lead
• • C—CHEMISTRY; METALLURGY
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  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C5/00—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms
  • C07C5/02—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation
  • C07C5/10—Preparation of hydrocarbons from hydrocarbons containing the same number of carbon atoms by hydrogenation of aromatic six-membered rings
  • C07C5/11—Partial hydrogenation
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  • 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
  • C10G45/58—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to change the structural skeleton of some of the hydrocarbon content without cracking the other hydrocarbons present, e.g. lowering pour point; Selective hydrocracking of normal paraffins
  • C10G45/68—Aromatisation of hydrocarbon oil fractions
• • 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
  • B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
  • B01J2229/30—After treatment, characterised by the means used
  • B01J2229/37—Acid treatment
• • B—PERFORMING OPERATIONS; TRANSPORTING
  • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
  • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
  • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
  • B01J37/28—Phosphorising
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2529/00—Catalysts comprising molecular sieves
  • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
  • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2529/00—Catalysts comprising molecular sieves
  • C07C2529/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites, pillared clays
  • C07C2529/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
  • C07C2529/40—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the pentasil type, e.g. types ZSM-5, ZSM-8 or ZSM-11
• • C—CHEMISTRY; METALLURGY
  • C07—ORGANIC CHEMISTRY
  • C07C—ACYCLIC OR CARBOCYCLIC COMPOUNDS
  • C07C2529/00—Catalysts comprising molecular sieves
  • C07C2529/87—Gallosilicates; Aluminogallosilicates; Galloborosilicates
• • 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
  • C10G2300/10—Feedstock materials
  • C10G2300/1033—Oil well production fluids
• • 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
  • C10G2300/10—Feedstock materials
  • C10G2300/1037—Hydrocarbon fractions
  • C10G2300/1044—Heavy gasoline or naphtha having a boiling range of about 100 - 180 °C
• • 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
  • C10G2300/10—Feedstock materials
  • C10G2300/1037—Hydrocarbon fractions
  • C10G2300/1048—Middle distillates
• • 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
  • C10G2300/10—Feedstock materials
  • C10G2300/1037—Hydrocarbon fractions
  • C10G2300/1048—Middle distillates
  • C10G2300/1051—Kerosene having a boiling range of about 180 - 230 °C
• • 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
  • C10G2300/10—Feedstock materials
  • C10G2300/1037—Hydrocarbon fractions
  • C10G2300/1048—Middle distillates
  • C10G2300/1055—Diesel having a boiling range of about 230 - 330 °C
• • 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
  • C10G2300/10—Feedstock materials
  • C10G2300/1037—Hydrocarbon fractions
  • C10G2300/1048—Middle distillates
  • C10G2300/1059—Gasoil having a boiling range of about 330 - 427 °C
• • 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
  • C10G2300/20—Characteristics of the feedstock or the products
  • C10G2300/30—Physical properties of feedstocks or products
  • C10G2300/301—Boiling range
• • 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
  • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
  • C10G2400/30—Aromatics

Definitions

• the present invention relates to a catalyst for producing monocyclic aromatic hydrocarbons and a method for producing monocyclic aromatic hydrocarbons that enable the production of monocyclic aromatic hydrocarbons from an oil containing a large amount of polycyclic aromatic hydrocarbons.
• LCO Light cycle oil
• monocyclic aromatic hydrocarbons of 6 to 8 carbon number such as benzene, toluene, xylene and ethylbenzene
• Patent Documents 1 to 3 propose methods that use zeolite catalysts to produce monocyclic aromatic hydrocarbons from the polycyclic aromatic hydrocarbons contained in large amounts within LCO and the like.
• Examples of known methods for improving the hydrothermal stability include a method that uses a zeolite having a high Si/Al ratio, a method in which the catalyst is subjected to a preliminary hydrothermal treatment to stabilize the catalyst, such as USY zeolite, a method in which phosphorus is added to a zeolite, a method in which a rare earth metal is added to a zeolite, and a method that involves improving the structure-directing agent used during the synthesis of a zeolite.
• the addition of phosphorus not only improves the hydrothermal stability, but also provides other known effects such as an improvement in selectivity due to suppression of carbon matter deposition during fluid catalytic cracking, and an improvement in the abrasion resistance of the binder. Accordingly, this method is frequently applied to catalysts used in catalytic cracking reactions.
• Examples of catalytic cracking catalysts prepared by adding phosphorus to a zeolite include those disclosed in Patent Documents 4 to 6.
• Patent Document 4 discloses a method for producing olefins from naphtha using a catalyst containing ZSM-5 to which has been added phosphorus, as well as gallium, germanium and/or tin.
• phosphorus is added for the purposes of suppressing the production of methane and aromatics in order to enhance the selectivity for olefin production, and ensuring a high degree of activity even for a short contact time, thereby improving the yield of olefins.
• Patent Document 5 discloses a method for producing olefins in a high yield from heavy hydrocarbons by using a catalyst prepared by supporting phosphorus on ZSM-5 containing zirconium and a rare earth element, and a catalyst containing a USY zeolite, an REY zeolite, kaolin, silica and alumina.
• Patent Document 6 discloses a method for producing ethylene and propylene in a high yield by transforming hydrocarbons using a catalyst containing ZSM-5 having phosphorus and a transition metal element supported thereon.
• Patent Document 6 discloses the yields for olefins (ethylene and propylene) and BTX (benzene, toluene and xylene), and whereas the yield for the olefins was 40% by mass, the yield for BTX was a low value of approximately 6% by mass.
• a catalyst for producing monocyclic aromatic hydrocarbons that is capable of producing monocyclic aromatic hydrocarbons of 6 to 8 carbon number in a high yield from a feedstock oil containing polycyclic aromatic hydrocarbons, and also capable of preventing any deterioration over time in the yield of the monocyclic aromatic hydrocarbons is currently not known.
• An object of the present invention is to provide a catalyst for producing monocyclic aromatic hydrocarbons and a method for producing monocyclic aromatic hydrocarbons that enable the production of monocyclic aromatic hydrocarbons of 6 to 8 carbon number in a high yield from a feedstock oil containing polycyclic aromatic hydrocarbons, and also enable the prevention of any deterioration over time in the yield of the monocyclic aromatic hydrocarbons of 6 to 8 carbon number.
• a catalyst for producing monocyclic aromatic hydrocarbons used for producing monocyclic aromatic hydrocarbons of 6 to 8 carbon number from a feedstock oil having a 10 volume % distillation temperature of at least 140° C. and an end point temperature of not more than 400° C., or a feedstock oil having a 10 volume % distillation temperature of at least 140° C. and a 90 volume % distillation temperature of not more than 350° C., wherein
• the catalyst contains a crystalline aluminosilicate, gallium and/or zinc, and phosphorus, and the amount of phosphorus supported on the crystalline aluminosilicate is within a range from 0.1 to 1.9% by mass based on the mass of the crystalline aluminosilicate.
• a catalyst for producing monocyclic aromatic hydrocarbons used for producing monocyclic aromatic hydrocarbons of 6 to 8 carbon number from a feedstock oil having a 10 volume % distillation temperature of at least 140° C. and an end point temperature of not more than 400° C., or a feedstock oil having a 10 volume % distillation temperature of at least 140° C. and a 90 volume % distillation temperature of not more than 360° C., wherein
• the catalyst contains a crystalline aluminosilicate, gallium and/or zinc, and phosphorus, and the amount of phosphorus is within a range from 0.1 to 5.0% by mass based on the mass of the catalyst.
• the catalyst for producing monocyclic aromatic hydrocarbons and the method for producing monocyclic aromatic hydrocarbons of 6 to 8 carbon number according to the present invention enable the production of monocyclic aromatic hydrocarbons of 6 to 8 carbon number in a high yield from a feedstock oil containing polycyclic aromatic hydrocarbons, and also enable the prevention of any deterioration over time in the yield of the monocyclic aromatic hydrocarbons of 6 to 8 carbon number.
• the catalyst for producing monocyclic aromatic hydrocarbons according to the present invention (hereinafter often referred to as “the catalyst”) is used for producing monocyclic aromatic hydrocarbons of 6 to 8 carbon number (hereinafter often abbreviated as “monocyclic aromatic hydrocarbons”) from a feedstock oil containing polycyclic aromatic hydrocarbons and saturated hydrocarbons, and contains a crystalline aluminosilicate, gallium and phosphorus.
• medium pore size zeolites such as zeolites with MFI, MEL, TON, MTT, MRE, FER, AEL and EUO type crystal structures are preferred, and in terms of maximizing the yield of monocyclic aromatic hydrocarbons, pentasil-type zeolites are more preferred, and zeolites with MFI-type and/or MEL-type crystal structures are particularly desirable.
• MFI-type and MEL-type zeolites are included within the conventional zeolite structures published by The Structure Commission of the International Zeolite Association (Atlas of Zeolite Structure Types, W. M. Meiyer and D. H. Olson (1978), distributed by Polycrystal Book Service, Pittsburgh, Pa. (USA)).
• the amount of the crystalline aluminosilicate within the catalyst is preferably within a range from 10 to 95% by mass, more preferably from 20 to 80% by mass, and still more preferably from 25 to 70% by mass. Provided the amount of the crystalline aluminosilicate is not less than 10% by mass and not more than 95% by mass, a satisfactorily high level of catalytic activity can be achieved.
• Examples of the form of the gallium contained within the catalyst of the present invention include catalysts in which the gallium is incorporated within the lattice framework of the crystalline aluminosilicate (crystalline aluminogallosilicates), catalysts in which gallium is supported on the crystalline aluminosilicate (gallium-supporting crystalline aluminosilicates), and catalysts including both of these forms.
• a crystalline aluminogallosilicate has a structure in which SiO 4 , AlO 4 and GaO 4 structures adopt tetrahedral coordination within the framework.
• a crystalline aluminogallosilicate can be obtained, for example, by gel crystallization via hydrothermal synthesis, by a method in which gallium is inserted into the lattice framework of a crystalline aluminosilicate, or by a method in which aluminum is inserted into the lattice framework of a crystalline gallosilicate.
• a gallium-supporting crystalline aluminosilicate can obtained by supporting gallium on a crystalline aluminosilicate using a conventional method such as an ion-exchange method or impregnation method.
• a conventional method such as an ion-exchange method or impregnation method.
• gallium source used in these methods include gallium salts such as gallium nitrate and gallium chloride, and gallium oxide.
• the amount of gallium within the catalyst of the present invention is preferably within a range from 0.01 to 5.0% by mass.
• Examples of the form of the zinc contained within the catalyst of the present invention include catalysts in which the zinc is incorporated within the lattice framework of the crystalline aluminosilicate (crystalline aluminozincosilicates), catalysts in which zinc is supported on the crystalline aluminosilicate (zinc-supporting crystalline aluminosilicates), and catalysts including both of these forms.
• a crystalline aluminozincosilicate has a structure in which SiO 4 , AlO 4 and ZnO 4 structures exist within the framework.
• a crystalline aluminozincosilicate can be obtained, for example, by gel crystallization via hydrothermal synthesis, by a method in which zinc is inserted into the lattice framework of a crystalline aluminosilicate, or by a method in which aluminum is inserted into the lattice framework of a crystalline zincosilicate.
• a zinc-supporting crystalline aluminosilicate can obtained by supporting zinc on a crystalline aluminosilicate using a conventional method such as an ion-exchange method or impregnation method.
• a conventional method such as an ion-exchange method or impregnation method.
• zinc source used in these methods, and examples include zinc salts such as zinc nitrate and zinc chloride, and zinc oxide.
• the amount of zinc within the catalyst of the present invention is preferably within a range from 0.01 to 5.0% by mass.
• the catalyst of the present invention may be a catalyst that contains either one of gallium or zinc, or a catalyst that contains both gallium and zinc. Further, the catalyst may also contain one or more other metals in addition to the gallium and/or zinc.
• the amount of phosphorus supported on the crystalline aluminosilicate in the catalyst of the present invention is preferably within a range from 0.1 to 1.9% by mass. Moreover, the lower limit for this range is more preferably at least 0.2% by mass, whereas the upper limit is more preferably not more than 1.5% by mass, and still more preferably not more than 1.2% by mass.
• the amount of phosphorus supported on the crystalline aluminosilicate is at least 0.1% by mass, deterioration over time in the yield of the monocyclic aromatic hydrocarbons can be prevented, whereas ensuring that the amount is not more than 1.9% by mass enables the yield of the monocyclic aromatic hydrocarbons to be increased.
• the upper limit for the amount of phosphorus within the catalyst of the present invention is considerably lower than the upper limit for the amount of phosphorus within the catalysts disclosed in Patent Documents 4 to 6. It is thought that one reason for this difference is the fact that the feedstock oil for the reaction in which the catalyst of the present invention is used contains a large amount of polycyclic aromatic hydrocarbons and exhibits relatively low reactivity. If the amount of phosphorus is increased too much, then the feedstock oil is even less likely to undergo reaction and the aromatic activity decreases, resulting in a deterioration in the yield of the monocyclic aromatic hydrocarbons.
• the feedstock oils in Patent Documents 4 to 6 are heavy, have large molecular weights and are adsorbed readily onto the catalyst, and are therefore cracked more readily than fractions such as LCO. Moreover, because cracking to form light olefins is relatively easy, even if a large amount of phosphorus is supported on the catalyst and the aromatic activity decreases to some extent, this does not cause significant problems.
• a solution prepared by dissolving phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate or another water-soluble phosphate salt in water at an arbitrary concentration can be used particularly favorably.
• the catalyst of the present invention can be obtained by calcining (at a calcination temperature of 300 to 900° C.) an above-mentioned phosphorus-supporting crystalline aluminogallosilicate or crystalline aluminozincosilicate, or a crystalline aluminosilicate having gallium/zinc and phosphorus supported thereon.
• the catalyst of the present invention is used in the form of a powder, granules or pellets or the like, depending on the reaction format.
• a powder is used in the case of a fluidized bed, whereas granules or pellets are used in the case of a fixed bed.
• the average particle size of the catalyst used in a fluidized bed is preferably within a range from 30 to 180 ⁇ m, and more preferably from 50 to 100 ⁇ m.
• the bulk density of the catalyst used in a fluidized bed is preferably within a range from 0.4 to 1.8 g/cc, and more preferably from 0.5 to 1.0 g/cc.
• the average particle size describes the particle size at which the particle size distribution obtained by classification using sieves reaches 50% by mass, whereas the bulk density refers to the value measured using the method prescribed in JIS R 9301-2-3.
• an inert oxide may be added to the crystalline aluminosilicate or catalyst as a binder or the like, with the resulting mixture then molded using any of various molding apparatus.
• the catalyst of the present invention contains an inorganic oxide such as a binder
• a compound that contains phosphorus may also be used as the binder.
• the catalyst may be produced by mixing the binder and the crystalline aluminosilicate, and subsequently adding the gallium and/or zinc and the phosphorus, or by mixing the binder and the gallium- and/or zinc-supporting crystalline aluminosilicate, or mixing the binder and the crystalline aluminogallosilicate and/or crystalline aluminozincosilicate, and subsequently adding the phosphorus.
• the amount of phosphorus relative to the total mass of the catalyst is preferably within a range from 0.1 to 5.0% by mass, and the lower limit for this range is more preferably at least 0.2% by mass, whereas the upper limit is more preferably not more than 3.0% by mass, and still more preferably not more than 2.0% by mass.
• the method for producing monocyclic aromatic hydrocarbons according to the present invention involves bringing a feedstock oil into contact with the above-mentioned catalyst to effect a reaction.
• saturated hydrocarbons function as hydrogen donor sources, and a hydrogen transfer reaction from the saturated hydrocarbons is used to convert polycyclic aromatic hydrocarbons into monocyclic aromatic hydrocarbons.
• the feedstock oil used in the present invention is either an oil having a 10 volume % distillation temperature of at least 140° C. and an end point temperature of not more than 400° C., or an oil having a 10 volume % distillation temperature of at least 140° C. and a 90 volume % distillation temperature of not more than 360° C.
• an oil having a 10 volume % distillation temperature of less than 140° C. the reaction involves production of BTX from light compounds, which is unsuitable in the present embodiment, and therefore the 10 volume % distillation temperature is preferably at least 140° C., and more preferably 150° C. or higher. Further, if an oil having an end point temperature exceeding 400° C.
• the end point temperature of the feedstock oil is preferably not more than 400° C., and more preferably 380° C. or lower.
• the 90 volume % distillation temperature for the feedstock oil is preferably not more than 360° C., and more preferably 350° C. or lower.
• the 10 volume % distillation temperature, the 90 volume % distillation temperature and the end point temperature refer to values measured in accordance with the methods prescribed in JIS K2254 “Petroleum products—determination of distillation characteristics”.
• feedstock oils having a 10 volume % distillation temperature of at least 140° C. and an end point temperature of not more than 400° C. or feedstock oils having a 10 volume % distillation temperature of at least 140° C. and a 90 volume % distillation temperature of not more than 350° C.
• cracked gas oils (LCO) produced in a fluid catalytic cracking coal liquefaction oil, hydrocracked oil from heavy oils, straight-run kerosene, straight-nm gas oil, coker kerosene, coker gas oil, and hydrocracked oil from oil sands.
• cracked gas oils (LCO) produced in a fluid catalytic cracking are particularly desirable.
• the amount of polycyclic aromatic hydrocarbons (the polycyclic aromatic content) within the feedstock oil is preferably not more than 50 volume %, and more preferably 30 volume % or less.
• the polycyclic aromatic content describes the combined total of the amount of bicyclic aromatic hydrocarbons (the bicyclic aromatic content) and the amount of tricyclic and higher aromatic hydrocarbons (the tricyclic and higher aromatic content) measured in accordance with JPI-5S-49 “Petroleum Products—Determination of Hydrocarbon Types—High Performance Liquid Chromatography”.
• reaction format used for bringing the feedstock oil into contact with the catalyst for reaction examples include fixed beds, moving beds and fluidized beds.
• a fluidized bed is preferred as it enables the coke fraction adhered to the catalyst to be removed in a continuous manner and enables the reaction to proceed in a stable manner.
• a continuous regeneration-type fluidized bed in which the catalyst is circulated between the reactor and a regenerator, thereby continuously repeating a reaction-regeneration cycle, is particularly desirable.
• the feedstock oil that makes contact with the catalyst is preferably in a gaseous state. Further, the feedstock may be diluted with a gas if required. Furthermore, in those cases where unreacted feedstock occurs, this may be recycled as required.
• reaction temperature during contact of the feedstock oil with the catalyst for reaction
• a reaction temperature of 350 to 700° C. is preferred.
• the lower limit is more preferably 450° C. or higher.
• an upper limit temperature of not more than 650° C. is preferable as it is not only more advantageous from an energy perspective, but also enables reliable regeneration of the catalyst.
• the reaction pressure during contact of the feedstock oil with the catalyst for reaction is preferably not more than 1.0 MPaG. Provided the reaction pressure is not more than 1.0 MPaG, the generation of by-product light gases can be prevented, and the pressure resistance required for the reaction apparatus can be lowered.
• the contact time between the feedstock oil and the catalyst there are no particular limitations on the contact time between the feedstock oil and the catalyst, provided the desired reaction proceeds satisfactorily, but in terms of the gas transit time across the catalyst, a time of 1 to 300 seconds is preferred.
• the lower limit for this time is more preferably at least 5 seconds, and the upper limit is more preferably 150 seconds or less.
• the contact time is at least 1 second, a reliable reaction can be achieved, whereas provided the contact time is not more than 300 seconds, deposition of carbon matter on the catalyst due to coking or the like can be suppressed. Further, the amount of light gas generated by cracking can also be suppressed.
• hydrogen transfer occurs from saturated hydrocarbons to the polycyclic aromatic hydrocarbons, and the polycyclic aromatic hydrocarbons undergo partial hydrogenation and ring opening, yielding monocyclic aromatic hydrocarbons.
• the yield of monocyclic aromatic hydrocarbons is preferably at least 15% by mass, more preferably at least 20% by mass, and still more preferably 25% by mass or greater. If the yield of monocyclic aromatic hydrocarbons is less than 15% by mass, then the concentration of the target compounds within the reaction product is low, and the efficiency with which those compounds can be recovered tends to deteriorate.
• the solution (B) was added gradually to the solution (A).
• the resulting mixture was stirred vigorously for 15 minutes using a mixer, thereby breaking up the gel and forming a uniform fine milky mixture.
• This mixture was placed in a stainless steel autoclave, and a crystallization operation was performed under conditions including a temperature of 165° C., a reaction time of 72 hours, a stirring rate of 100 rpm, and under self-generated pressure.
• the product was filtered, the solid product was recovered, and an operation of washing the solid product and then performing filtration was repeated 5 times, using a total of approximately 5 liters of deionized water in the 5 times of operations.
• the solid material obtained upon the final filtration was dried at 120° C., and was then calcined under a stream of air at 550° C. for 3 hours.
• a 30% by mass aqueous solution of ammonium nitrate was added to the calcined product in a ratio of 5 mL of the aqueous solution per 1 g of the calcined product, and after heating at 100° C. with constant stirring for 2 hours, the mixture was filtered and washed with water. This operation was performed 4 times in total, and the product was then dried for 3 hours at 120° C., yielding an ammonium-type crystalline aluminosilicate. Subsequently, the product was calcined for 3 hours at 780° C., yielding a proton-type crystalline aluminosilicate.
• the obtained gallium-supporting crystalline aluminosilicate was impregnated with 30 g of an aqueous solution of diammonium hydrogen phosphate in order to support 0.2% by mass of phosphorus on the aluminosilicate (based on a value of 100% for the total mass of the crystalline aluminosilicate), and the resulting product was then dried at 120° C. Subsequently, the product was calcined for 3 hours at 780° C. under a stream of air, yielding a catalyst containing the crystalline aluminosilicate, gallium and phosphorus.
• Tablet molding was performed by applying a pressure of 39.2 MPa (400 kgf) to the obtained catalyst, and the resulting tablets were subjected to coarse crushing and then classified using a 20 to 28 mesh size, thus yielding a granular catalyst 1 (hereinafter referred to as the “granulated catalyst 1”).
• a granular catalyst 2 (hereinafter referred to as the “granulated catalyst 2”) was obtained in the same manner as that described in catalyst preparation example 1.
• a granular catalyst 3 (hereinafter referred to as the “granulated catalyst 3”) was obtained in the same manner as that described in catalyst preparation example 1.
• a granular catalyst 5 (hereinafter referred to as the “granulated catalyst 5”) was obtained in the same manner as that described in catalyst preparation example 1.
• sodium silicate J Sodium Silicate No. 3, SiO 2 : 28 to 30% by mass, Na: 9 to 10% by mass, remainder: water, manufactured by Nippon Chemical Industrial Co., Ltd.
• pure water was added dropwise to a dilute sulfuric acid solution to prepare a silica sol aqueous solution (SiO 2 concentration: 10.2%). Meanwhile, distilled water was added to 20.4 g of the catalyst prepared
• the zeolite slurry was mixed with 300 g of the silica sol aqueous solution, and the resulting slurry was spray dried at 250° C., yielding a spherically shaped catalyst. Subsequently, the catalyst was calcined for 3 hours at 600° C., yielding a powdered catalyst 6 (hereinafter referred to as the “powdered catalyst 6”) having an average particle size of 85 ⁇ m and a bulk density of 0.75 g/cc.
• a granular catalyst 7 (hereinafter referred to as the “granulated catalyst 7”) was obtained in the same manner as that described in catalyst preparation example 1.
• a granular catalyst 8 (hereinafter referred to as the “granulated catalyst 8”) was obtained in the same manner as that described in catalyst preparation example 1.
• a feedstock oil having the properties shown in Table 1 was brought into contact with the granulated catalyst and reacted under conditions including a reaction temperature of 550° C. and a reaction pressure of 0 MPaG. During the reaction, nitrogen was introduced as a diluent so that the contact time between the feedstock oil and the granulated catalyst was 7 seconds.
• the heavy fraction refers to hydrocarbons of 6 or more carbon number other than the monocyclic aromatic hydrocarbons of 6 to 8 carbon number
• the light naphtha refers to hydrocarbons of 5 or 6 carbon number
• the liquefied petroleum gas refers to hydrocarbons of 3 or 4 carbon number
• the cracked gas refers to hydrocarbons of not more than 2 carbon number.
• a feedstock oil having the properties shown in Table 1 was brought into contact with the powdered catalyst and reacted under conditions including a reaction temperature of 550° C. and a reaction pressure of 0.1 MPaG.
• the powdered catalyst was packed in a reaction tube with a diameter of 60 mm.
• nitrogen was introduced as a diluent so that the contact time between the feedstock oil and the powdered catalyst was 10 seconds.
• the heavy fraction refers to hydrocarbons of 6 or more carbon number other than the monocyclic aromatic hydrocarbons of 6 to 8 carbon number
• the light naphtha refers to hydrocarbons of 5 or 6 carbon number
• the liquefied petroleum gas refers to hydrocarbons of 3 or 4 carbon number
• the cracked gas refers to hydrocarbons of not more than 2 carbon number.
• the granulated catalysts 1 to 5 and 8 and the powdered catalyst 6 were each subjected to a hydrothermal treatment under conditions including a treatment temperature of 650° C. and a treatment time of 6 hours in a 100% by mass steam atmosphere, thus preparing pseudo-degraded catalysts 1 to 6 and 8 that had undergone a simulated hydrothermal degradation.
• a value was calculated for the ratio of the amount (% by mass) of monocyclic aromatic hydrocarbons of 6 to 8 carbon number in the catalytic activity evaluation following hydrothermal degradation (evaluation 3) relative to the amount (% by mass) of monocyclic aromatic hydrocarbons of 6 to 8 carbon number in the initial reaction catalytic activity evaluation (evaluation 1 or evaluation 2) (namely, [amount (% by mass) of monocyclic aromatic hydrocarbons of 6 to 8 carbon number in evaluation 3]/[amount (% by mass) of monocyclic aromatic hydrocarbons of 6 to 8 carbon number in evaluation 1 or evaluation 2]), and this value was used to determine the degree of catalyst degradation.
• the results are summarized in Table 2. A larger value for this property indicates superior resistance to catalyst degradation.
• Examples 1 to 6 which employed the granulated catalysts 1 to 5 and the powdered catalyst 6 respectively, exhibited favorable initial reaction catalytic activity and favorable catalytic activity following hydrothermal degradation, and the monocyclic aromatic hydrocarbons of 6 to 8 carbon number which are objective products in the present embodiment were able to be obtained in high yield, both during the initial reaction and following hydrothermal degradation.
• Comparative Example 2 revealed that if a catalyst with no phosphorus supported thereon is used, despite the yield of monocyclic aromatic hydrocarbons of 6 to 8 carbon number is favorable during the initial reaction, the yield decreases significantly following hydrothermal degradation, and the deterioration in the catalyst is marked, making the catalyst impractical.

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