EP2617697B1 - Verfahren zur herstellung eines aromatischen kohlenwasserstoffs - Google Patents

Verfahren zur herstellung eines aromatischen kohlenwasserstoffs Download PDF

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Publication number
EP2617697B1
EP2617697B1 EP11825182.6A EP11825182A EP2617697B1 EP 2617697 B1 EP2617697 B1 EP 2617697B1 EP 11825182 A EP11825182 A EP 11825182A EP 2617697 B1 EP2617697 B1 EP 2617697B1
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EP
European Patent Office
Prior art keywords
aromatic hydrocarbons
naphthalene
catalyst
monocyclic aromatic
fraction
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EP11825182.6A
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English (en)
French (fr)
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EP2617697A1 (de
EP2617697A4 (de
Inventor
Shinichiro Yanagawa
Ryoji Ida
Masahide Kobayashi
Yasuyuki Iwasa
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Eneos Corp
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JX Nippon Oil and Energy Corp
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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
    • C10G11/00—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils
    • C10G11/02—Catalytic cracking, in the absence of hydrogen, of hydrocarbon oils characterised by the catalyst used
    • C10G11/04—Oxides
    • C10G11/05—Crystalline alumino-silicates, e.g. molecular sieves
    • 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
    • C10G35/00—Reforming naphtha
    • C10G35/04—Catalytic reforming
    • C10G35/06—Catalytic reforming characterised by the catalyst used
    • C10G35/095—Catalytic reforming characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
    • 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
    • C10G45/44—Hydrogenation of the aromatic hydrocarbons
    • 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
    • C10G63/00—Treatment of naphtha by at least one reforming process and at least one other conversion process
    • C10G63/02—Treatment of naphtha by at least one reforming process and at least one other conversion process plural serial stages only
    • 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
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • 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
    • C10G69/00—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process
    • C10G69/02—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only
    • C10G69/08—Treatment of hydrocarbon oils by at least one hydrotreatment process and at least one other conversion process plural serial stages only including at least one step of reforming naphtha
    • 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
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • C10G2300/203—Naphthenic acids, TAN
    • 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 method for producing aromatic hydrocarbons.
  • LCO Light cycle oil
  • FCC fluid catalytic cracking
  • Patent Documents 1 to 3 suggest methods for producing monocyclic aromatic hydrocarbons from polycyclic aromatic hydrocarbons that are contained in LCO and the like in a large amount, by using a zeolite catalyst.
  • the invention was achieved in view of the circumstances described above, and it is an object of the invention to provide a method for producing aromatic hydrocarbons, by which monocyclic aromatic hydrocarbons having 6 to 8 carbon numbers can be produced in high yields from a feedstock containing polycyclic aromatic hydrocarbons, and also, other chemical products, for example, aromatic hydrocarbons other than the monocyclic aromatic hydrocarbons, can be produced.
  • the present inventors conducted thorough investigations in order to achieve the object described above, and as a result, they obtained the following findings.
  • LCO contains a large amount of polycyclic aromatic hydrocarbons
  • a relatively large amount of a heavy oil fraction having 9 or more carbon numbers can also be obtained in addition to the monocyclic aromatic hydrocarbons having 6 to 8 carbon numbers.
  • this heavy oil fraction an investigation has been conducted to merely find that the heavy oil fraction may be collected as a light oil/kerosene base material, or may be recycled as a feedstock of the monocyclic aromatic hydrocarbons.
  • the present inventors analyzed in detail the components of the heavy oil fraction in order to promote effective utilization of the heavy oil fraction, and as a result, the inventors found that the heavy oil fraction contains a large proportion of naphthalene or alkylnaphthalenes. Further, based on such findings, the inventors further conducted investigations regarding the production of naphthalene as a chemical product, in parallel to the production of the monocyclic aromatic hydrocarbons, and as a result, the inventors achieved the invention.
  • the method for producing aromatic hydrocarbons of the invention includes a process according to claim 1.
  • the naphthalene collection step is preferably a step of separating and collecting methylnaphthalene and/or dimethylnaphthalene, and naphthalene.
  • the method for producing aromatic hydrocarbons preferably includes:
  • the apparatus for separating and collecting naphthalene compounds including naphthalene in the naphthalene collecting step is preferably a distillation apparatus.
  • the crystalline aluminosilicate contain, as main components, a zeolite with medium-sized pores and/or a zeolite with large-sized pores.
  • the reaction temperature employed is a temperature ranging from 400°C to 650°C.
  • the reaction pressure employed is a pressure ranging from 0.1 MPaG to 1.5 MPaG
  • the contact time for bringing the feedstock into contact with the catalyst for monocyclic aromatic hydrocarbon production in the cracking reforming reaction step to a period ranging from 5 to 150 seconds.
  • monocyclic aromatic hydrocarbons having 6 to 8 carbon numbers can be produced with a relatively high yield from a feedstock including polycyclic aromatic hydrocarbons, and in addition, naphthalene compounds including naphthalene can be produced as other chemical products.
  • FIG. 1 is a diagram for explaining an embodiment of the method for producing aromatic hydrocarbons of the invention.
  • FIG. 1 is a diagram for explaining an embodiment of the method for producing aromatic hydrocarbons of the invention, and the method for producing aromatic hydrocarbons of the present embodiment is a method for producing monocyclic aromatic hydrocarbons having 6 to 8 carbon numbers from a feedstock, and also producing naphthalene compounds including naphthalene.
  • the method for producing aromatic hydrocarbons of the present embodiment preferably includes, as shown in FIG 1 :
  • a feedstock is brought into contact with a catalyst for monocyclic aromatic hydrocarbon production
  • polycyclic aromatic hydrocarbons are partially hydrogenated by a hydrogen transfer reaction from saturated hydrocarbons by using the saturated hydrocarbons included in the feedstock as a hydrogen donating source
  • the polycyclic aromatic hydrocarbons are converted to monocyclic aromatic hydrocarbons by ring-opening.
  • conversion to monocyclic aromatic hydrocarbons can also be achieved by cyclizing and dehydrogenating saturated hydrocarbons obtainable from the feedstock or in a cracking step.
  • monocyclic aromatic hydrocarbons having 6 to 8 carbon numbers can also be obtained by cracking monocyclic aromatic hydrocarbons having 9 or more carbon numbers.
  • a product including monocyclic aromatic hydrocarbons having 6 to 8 carbon numbers and a heavy oil fraction having 9 or more carbon numbers is obtained.
  • This product includes, in addition to the monocyclic aromatic hydrocarbons and the heavy oil fraction, hydrogen, methane, ethane, ethylene, LPG (propane, propylene, butane, butene and the like), and the like.
  • the heavy oil fraction includes large amounts of naphthalene, methylnaphthalene, and dimethylnaphthalene. Meanwhile, in the present specification, these naphthalene, methylnaphthalene and dimethylnaphthalene are collectively described as "naphthalene compounds”.
  • components such as naphthenobenzenes, paraffins and naphthenes in the feedstock can be eliminated by producing monocyclic aromatic hydrocarbons, and polycyclic aromatic hydrocarbons can be converted mainly to naphthalene compounds with a high added value, such as naphthalene, methylnaphthalene and dimethylnaphthalene, which have fewer side chains, by cleaving alkyl side chains simultaneously with the conversion of polycyclic aromatic hydrocarbons to monocyclic aromatic hydrocarbons.
  • Light cycle oil or the like that is used as a main feedstock originally contains a large proportion of naphthalene compounds, but at the same time, contains large proportions of other components such as naphthenobenzenes and paraffins. Therefore, the content ratio of naphthalene compounds relative to the total amount of the feedstock is small, and it is very difficult to directly separate and purify naphthalene compounds from the feedstock. In the case of performing separation and purification of naphthalene compounds from the feedstock, high energy consumption type processes such as crystallization should be employed, which is not preferable.
  • the present cracking reforming reaction step enables the proportion of useful aromatic hydrocarbons that can be collected, to be increased to a large extent as described above.
  • the feedstock that is used is an oil having a 10 vol% distillation temperature of 140°C or higher and a 90 vol% distillation temperature of 380°C or lower. Since oil having a 10 vol% distillation temperature of lower than 140°C is light, monocyclic aromatic hydrocarbons are produced by very light fraction, and the oil is not suitable for the present embodiment. Furthermore, when an oil having a 90 vol% distillation temperature of higher than 380°C is used, not only the yield of monocyclic aromatic hydrocarbons is lowered, but also the amount of coke deposition on the catalyst for monocyclic aromatic hydrocarbon production increases, and the catalytic activity tends to undergo a rapid decrease.
  • the 10 vol% distillation temperature of the feedstock is preferably 150°C or higher, and the 90 vol% distillation temperature of the feedstock is preferably 360°C or lower.
  • the upper limit of the 10 vol% distillation temperature and the lower limit of the 90 vol% distillation temperature of the feedstock are not particularly limited, but from the viewpoint that monocyclic aromatic hydrocarbons having 6 to 8 carbon numbers and naphthalene compounds can be efficiently produced, the 10 vol% distillation temperature is preferably 210°C or lower, and the 90 vol% distillation temperature is preferably 240°C or higher.
  • vol% distillation temperature and 90 vol% distillation temperature as used herein mean values measured according to JIS K2254 "Petroleum products - Distillation test methods".
  • Examples of the feedstock having a 10 vol% distillation temperature of 140°C or higher and a 90 vol% distillation temperature of 380°C or lower include LCO produced by a FCC units, a hydrogenated purified oil of LCO, other cracked light oils such as hydrogenated cracked light oil and thermally cracked light oil, coal liquefied oil, heavy oil hydrogenated cracked purified oil, straight run kerosene, straight run light oil, coker kerosene, coker light oil, and purified oil obtained by hydrogenation cracking oil sand.
  • the content of polycyclic aromatic hydrocarbons (polycyclic aromatic content) in the feedstock is preferably 50 vol% or less, and more preferably 40 vol% or less.
  • the polycyclic aromatic content in the feedstock may be adjusted to, for example, 50 vol% or more.
  • the content of aromatic hydrocarbons having 3 or more rings is preferably set to 30 vol% or less, and more preferably set to 15 vol% or less.
  • polycyclic aromatic content means the total value of the content of bicyclic aromatic hydrocarbons (bicyclic aromatic content) and the content of aromatic hydrocarbons with 3 or more rings (tricyclic or higher-cyclic aromatic content), which are measured according to JPI-5S-49 "Petroleum products - Hydrocarbon type test methods - high performance liquid chromatographic method", or analyzed by an FID gas chromatographic method.
  • JPI-5S-49 Petroleum products - Hydrocarbon type test methods - high performance liquid chromatographic method
  • FID gas chromatographic method analyzed by an FID gas chromatographic method.
  • Examples of the reaction mode employed when the feedstock is brought into contact with a catalyst for monocyclic aromatic hydrocarbons to react therewith include a fixed bed, a mobile bed, and a fluidized bed.
  • a fluidized bed which is capable of continuously removing the coke component adhering to the catalyst and is capable of stably carrying out the reaction is preferred.
  • a continuously regenerative type fluidized bed in which a catalyst is circulated between a reactor and a regenerator so that reaction-regeneration can be continuously repeated, is particularly preferred.
  • the feedstock is preferably in a gas phase.
  • the feedstock may also be diluted with a gas as necessary.
  • the catalyst for monocyclic aromatic hydrocarbon production contains a crystalline aluminosilicate.
  • the crystalline aluminosilicate is preferably a zeolite with medium-sized pores and/or a zeolite with large-sized pores.
  • the zeolite with medium-sized pores is a zeolite having a 10-membered ring skeletal structure, and examples of the zeolite with medium-sized pores include zeolites having AEL type, EUO type, FER type, HEU type, MEL type, MFI type, NES type, TON type, and WEI type crystal structures.
  • MFI type zeolite is preferred from the viewpoint that the yield of monocyclic aromatic hydrocarbons can be further increased.
  • the zeolite with large-sized pores is a zeolite having a 12-membered ring skeletal structure, and examples of the zeolite with large-sized pores include zeolites having AFI type, ATO type, BEA type, CON type, FAU type, GME type, LTL type, MOR type, MTW type, and OFF type crystal structures.
  • BEAtype zeolite is preferred.
  • a catalyst containing a crystalline aluminosilicate other than the MFI type or BEA type zeolite described above may also be used.
  • the crystalline aluminosilicate may also contain a zeolite with small-sized pores, having a 10-membered or fewer-membered ring skeletal structure, and a zeolite with ultra-large-sized pores, having a 14-membered or more-membered ring skeletal structure, in addition to the zeolite with medium-sized pores and the zeolite with large-sized pores.
  • examples of the zeolite with small-sized pores include zeolites having ANA type, CHAtype, ERI type, GIS type, KFI type, LTA type, NAT type, PAU type and YUG type crystal structures.
  • Examples of the zeolite with ultra-large-sized pores include zeolites having CLO type and VPI type crystal structures.
  • the content of the crystalline aluminosilicate in the catalyst for monocyclic aromatic hydrocarbon production is preferably 60 mass% to 100 mass%, more preferably 70 mass% to 100 mass%, and particularly preferably 90 mass% to 100 mass%, when the total amount of the catalyst for monocyclic aromatic hydrocarbon production is designated as 100 mass%.
  • the content of the crystalline aluminosilicate is 60 mass% or more, the yield of monocyclic aromatic hydrocarbons can be sufficiently increased. Furthermore, the yield of naphthalene compounds can also be raised to a relatively high level.
  • the content of the crystalline aluminosilicate in the catalyst for monocyclic aromatic hydrocarbon production is preferably 20 mass% to 60 mass%, more preferably 30 mass% to 60 mass%, and particularly preferably 35 mass% to 60 mass%, when the total amount of the catalyst for monocyclic aromatic hydrocarbon production is designated as 100 mass%.
  • the content of the crystalline aluminosilicate is 20 mass% or more, the yield of monocyclic aromatic hydrocarbons can be sufficiently increased. Furthermore, the yield of naphthalene compounds can also be raised to a relatively high level. Meanwhile, when the content of the crystalline aluminosilicate is more than 60 mass%, the content of a binder that can be incorporated into the catalyst is decreased, and the catalyst may not be suitable for fluidized bed applications.
  • the catalyst for monocyclic aromatic hydrocarbon production preferably contains phosphorus and/or boron.
  • the catalyst for monocyclic aromatic hydrocarbon production contains phosphorus and/or boron, a decrease in the yield of monocyclic aromatic hydrocarbons over time can be prevented, and coke production on the catalyst surface can be suppressed.
  • Examples of the method for incorporating phosphorus to the catalyst for monocyclic aromatic hydrocarbon production include a method of supporting phosphorus on a crystalline aluminosilicate, a crystalline aluminogallosilicate or a crystalline aluminozincosilicate, by an ion exchange method, an impregnation method or the like; a method of incorporating a phosphorus compound at the time of zeolite synthesis and substituting a portion in the skeleton of a crystalline aluminosilicate with phosphorus; and a method of using a crystallization accelerator containing phosphorus at the time of zeolite synthesis.
  • the phosphate ion-containing aqueous solution used at that time is not particularly limited, but solutions prepared by dissolving phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, and other water-soluble phosphates in water at arbitrary concentrations can be preferably used.
  • Examples of the method of incorporating boron into the catalyst for monocyclic aromatic hydrocarbon production include a method of supporting boron on a crystalline aluminosilicate, a crystalline aluminogallosilicate or a crystalline aluminozincosilicate, by an ion exchange method, an impregnation method or the like; a method of incorporating a boron compound at the time of zeolite synthesis and substituting a portion of the skeleton of a crystalline aluminosilicate with boron; and a method of using a crystallization accelerator containing boron at the time of zeolite synthesis.
  • the content of phosphorus and/or boron in the catalyst for monocyclic aromatic hydrocarbon production is preferably 0.1 mass% to 10 mass%, relative to the total weight of the catalyst, and the lower limit is more preferably 0.5 mass% or more, while the upper limit is more preferably 9 mass% or less, and particularly preferably 8 mass% or less.
  • the content of phosphorus and/or boron relative to the total weight of the catalyst is 0.1 mass% or more, a decrease in the yield of monocyclic aromatic hydrocarbons over time can be prevented, and when the content is 10 mass% or less, the yield of monocyclic aromatic hydrocarbons can be increased.
  • gallium and/or zinc can be incorporated as necessary.
  • the production proportion of monocyclic aromatic hydrocarbons can be further increased.
  • the form of gallium incorporation in the catalyst for monocyclic aromatic hydrocarbon production may be a form in which gallium is incorporated into the lattice skeleton of a crystalline aluminosilicate (crystalline aluminogallosilicate), a form in which gallium is supported on a crystalline aluminosilicate (gallium-supporting crystalline aluminosilicate), or both of them.
  • crystalline aluminosilicate crystalline aluminogallosilicate
  • gallium-supporting crystalline aluminosilicate gallium-supporting crystalline aluminosilicate
  • the form of zinc incorporation in the catalyst for monocyclic aromatic hydrocarbon production may be a form in which zinc is incorporated into the lattice skeleton of a crystalline aluminosilicate (crystalline aluminozincosilicate), a form in which zinc is supported on a crystalline aluminosilicate (zinc-supporting crystalline aluminosilicate), or both of them.
  • the crystalline aluminogallosilicate and crystalline aluminozincosilicate have a structure in which SiO 4 , AlO 4 and GaO 4 /ZnO 4 structures exist in the skeletal structure. Furthermore, the crystalline aluminogallosilicate and crystalline aluminozincosilicate are obtained by, for example, gel crystallization based on hydrothermal synthesis, a method of inserting gallium or zinc into the lattice skeleton of a crystalline aluminosilicate, or a method of inserting aluminum into the lattice skeleton of a crystalline gallosilicate or a crystalline zincosilicate.
  • the gallium-supporting crystalline aluminosilicate is a material in which gallium is supported on a crystalline aluminosilicate according to a known method such as an ion exchange method or an impregnation method.
  • the gallium source that is used at that time is not particularly limited, but examples thereof include gallium salts such as gallium nitrate and gallium chloride, and gallium oxide.
  • the zinc-supporting crystalline aluminosilicate is a compound in which zinc is supported on a crystalline aluminosilicate according to a known method such as an ion exchange method or an impregnation method.
  • the zinc source that is used at that time is not particularly limited, but examples thereof include zinc salts such as zinc nitrate and zinc chloride, and zinc oxide.
  • the content of gallium and/or zinc in the catalyst for monocyclic aromatic hydrocarbon production is preferably 0.01 mass% to 5.0 mass%, and more preferably 0.05 mass% to 1.5 mass%, relative to 100 mass% of the total amount of the catalyst.
  • the content of gallium and/or zinc is 0.01 mass% or greater, the production proportion of monocyclic aromatic hydrocarbons can be further increased.
  • the content is 5.0 mass% or less, the yield of monocyclic aromatic hydrocarbons can be further increased.
  • the catalyst for monocyclic aromatic hydrocarbon production is produced into, for example, a powder form, a particulate form, a pellet form or the like according to the reaction mode.
  • the catalyst in the case of a fluidized bed, the catalyst is produced in a powder form, and in the case of a fixed bed, the catalyst is produced in a particulate form or a pellet form.
  • the average particle size of the catalyst used in a fluidized bed is preferably 30 ⁇ m to 180 ⁇ m, and more preferably 50 ⁇ m to 100 ⁇ m.
  • the apparent density of the catalyst used in a fluidized bed is preferably 0.4 g/cc to 1.8 g/cc, and more preferably 0.5 g/cc to 1.0 g/cc.
  • the average particle size represents the particle size for a proportion of 50 mass% in a particle size distribution obtained by classification using sieves, and the apparent density is a value measured by the method of JIS Standards R9301-2-3.
  • an oxide which is inert to the catalyst is incorporated as a binder as necessary, and the mixture may be molded by using various molding machines.
  • the catalyst for monocyclic aromatic hydrocarbon production contains an inorganic oxide such as a binder
  • a binder containing phosphorus may also be used.
  • the reaction temperature at the time of bringing the feedstock into contact with the catalyst for monocyclic aromatic hydrocarbon production to react therewith is 400°C to 650°C, and more preferably 450°C to 650°C.
  • the reaction temperature is 400°C or higher, the reaction of the feedstock can be facilitated.
  • the reaction temperature is from 450°C to 650°C, the yield of monocyclic aromatic hydrocarbons can be sufficiently increased, and the yield of naphthalene compounds can also be raised to a relatively high level.
  • the reaction pressure employed when the feedstock is brought into contact with the catalyst for monocyclic aromatic hydrocarbon production to react therewith is from 0.1 MPaG to 1.5 MPaG.
  • the upper limit is more preferably set to 1.0 MPaG.
  • the reaction pressure is 1.5 MPaG or less, by-production of light gas can be suppressed, and also, pressure resistance of the reaction apparatus can be lowered.
  • the reaction pressure is from 0.1 MPaG to 1.5 MPaG, the yield of monocyclic aromatic hydrocarbons can be sufficiently increased, and the yield of naphthalene compounds can also be raised to a relatively high level.
  • the time for gas passage on the catalyst for monocyclic aromatic hydrocarbon production is 5 seconds or longer, while the upper limit is 150 seconds or shorter.
  • the contact time is 1 second or longer, the reaction can be achieved reliably, and when the contact time is 300 seconds or shorter, accumulation of carbon substances on the catalyst caused by coking or the like can be suppressed. Also, the amount of light gas generated by cracking can be suppressed.
  • the yield of monocyclic aromatic hydrocarbons can be sufficiently increased, and the yield of naphthalene compounds can also be raised to a relatively high level.
  • the product produced in the cracking reforming reaction step is separated into multiple fractions.
  • distillation apparatuses In order to separate the product into plural fractions, known distillation apparatuses and gas-liquid separation apparatuses may be used.
  • the distillation apparatuses include apparatuses that are capable of separating by distillation of multiple fractions by a multistage distillation apparatus such as a stripper.
  • the gas-liquid separation apparatuses include apparatuses each equipped with a gas-liquid separating tank, a product inlet pipe for introducing the product into the gas-liquid separating tank, a gas component discharge pipe provided in the upper part of the gas-liquid separating tank, and a liquid component discharge pipe provided in the lower part of the gas liquid separating tank.
  • the separation step includes separation of at least gas components and a liquid fraction, and the liquid fraction is further separated into plural fractions.
  • the liquid fraction is separated into LPG, a fraction containing monocyclic aromatic hydrocarbons, and a heavy oil fraction.
  • the catalyst powder and the like to be incorporated may be removed in the present step.
  • naphthalene compounds may be separated singly, or the heavy oil fraction may also be collectively fractionated without separating into plural fractions.
  • the boiling point range of the fraction containing monocyclic aromatic hydrocarbons having 6 to 8 carbon numbers is preferably 78°C to 150°C, and the boiling point range of the heavy oil fraction primarily containing naphthalene compounds is preferably 210°C to 270°C.
  • the purification and collection step purifies and collects the monocyclic aromatic hydrocarbons having 6 to 8 carbon numbers obtained in the separation step.
  • the liquid fraction is sufficiently fractionated in the separation step, and when monocyclic aromatic hydrocarbons having 6 to 8 carbon numbers are separated into benzene/toluene/xylene, a step of purifying and collecting the respective components is employed. Furthermore, when the monocyclic aromatic hydrocarbons having 6 to 8 carbon numbers are collectively fractionated, a step of collecting these monocyclic aromatic hydrocarbons, subsequently separating the hydrocarbons into benzene/toluene/xylene, and then purifying and collecting the respective components is employed.
  • the liquid fraction is not satisfactorily fractionated in the separation step, and when the monocyclic aromatic hydrocarbons having 6 to 8 carbon numbers are collected, the liquid fraction contains a large proportion of a fraction other than the monocyclic aromatic hydrocarbons, these fractions may be separated and supplied to, for example, the hydrogenation reaction step or naphthalene collection step that will be described below.
  • a fraction heavier than the monocyclic aromatic hydrocarbons is preferably supplied to the naphthalene collection step. This is because the heavy oil fraction having 9 or more carbon numbers contains polycyclic aromatic hydrocarbons as a main component, and contains a large proportion of naphthalene or alkylnaphthalenes in particular.
  • naphthalene compounds including at least naphthalene are separated and collected from a heavy oil fraction having 9 or more carbon numbers obtainable from the liquid fraction separated in the separation step.
  • this naphthalene collecting step in the case where the heavy oil fraction separated in the separation step is separated into a heavy oil fraction primarily containing naphthalene compounds in particular and a heavy oil fraction other than that, the heavy oil fraction containing naphthalene compounds is purified, and thus naphthalene compounds are separated and collected.
  • the separation step when the heavy oil fraction having 9 or more carbon numbers is collectively fractionated without dividing the heavy oil fraction having 9 or more carbon numbers into plural fractions, the heavy oil fraction is separated into a fraction containing naphthalene compounds, specifically naphthalene compounds including naphthalene, methylnaphthalene and dimethylnaphthalene, and a fraction other than that, and the naphthalene compounds including at least naphthalene are purified and collected.
  • naphthalene compounds specifically naphthalene compounds including naphthalene, methylnaphthalene and dimethylnaphthalene
  • distillation column distillation column
  • naphthalene can be separated with high purity, purified and collected by using only a known distillation apparatus such as that used in the separation step. For example, naphthalene can be purified to a purity of about 80% to 98% and then can be collected. Meanwhile, the purity of naphthalene thus collected is determined on the basis of reduction of the number and the production amount of components having a boiling point close to that of naphthalene that remains in the cracking reforming reaction step, and the performance of the distillation apparatus.
  • the naphthalene When naphthalene is collected with a purity of 95% or higher, the naphthalene can be dealt with as a product which is generally distributed as crude naphthalene and has a commercial value, and in regard to naphthalene with a purity of less than 95%, for example, about 80% to 95%, this can be made into crude naphthalene as a chemical product by performing a purification treatment later and increasing the purity to 95% or higher. Furthermore, a fraction having a purity of 95% or higher can also be subjected to a further purification treatment and can be converted to naphthalene with higher purity. Examples of the purification treatment methods in this case include crystallization.
  • naphthalene compounds other than naphthalene may be collectively separated, purified and collected as alkylnaphthalenes, or may be individually separated, purified and collected as methylnaphthalene, dimethylnaphthalene and the like.
  • methylnaphthalene and dimethylnaphthalene are respectively purified to a purity of about 80% to 95% and collected. Thereafter, the components are respectively purified to a purity demanded as chemical products.
  • naphthalene collecting step a fraction other than the desired naphthalene, methylnaphthalene and dimethylnaphthalene is also obtained.
  • This fraction is sent out of the system, and for example, after treatments such as purification are carried out as necessary, the fraction is used as a base material for light oil/kerosene.
  • the fraction is sent to the hydrogenation reaction step that will be described below, and after this step, the fraction is recycled.
  • the naphthalene collecting step is composed of a single step.
  • the step may be divided into multiple steps by providing a step of separating and collecting naphthalene from a heavy oil fraction having 9 or more carbon numbers, and then providing steps of respectively fractionating and collecting methylnaphthalene, dimethylnaphthalene and the like, and naphthalene, methylnaphthalene and dimethylnaphthalene may be respectively fractionated and collected.
  • a fraction other than these is used as a base material for light oil/kerosene, or is subjected to a hydrogenation reaction step or the like and then supplied to the feedstock for recycling.
  • this hydrogenation reaction step a portion or the entirety of the remaining fraction obtained after naphthalene has been separated in the naphthalene collecting step is supplied to this hydrogenation reaction step, and this fraction is hydrogenated.
  • these alkylnaphthalenes constitute the "remaining fraction obtained after naphthalene has been separated" as described above, and are supplied to the hydrogenation reaction step.
  • the remaining fraction obtained after naphthalene compounds have been separated which was not supplied to the hydrogenation reaction step, may also be used as a fuel base material for light oil/kerosene and the like.
  • the remaining fraction obtained by naphthalene compounds have been separated in the naphthalene collecting step, and hydrogen are supplied to a hydrogenation reactor, and at least a portion of the polycyclic aromatic hydrocarbons included in the remaining fraction obtained after naphthalene compounds have been separated is subjected to hydrogenation by using a hydrogenation catalyst.
  • the polycyclic aromatic hydrocarbons are not particularly limited, but it is preferable to hydrogenate the polycyclic aromatic hydrocarbons until the number of aromatic rings becomes 1 or less on the average.
  • the polycyclic aromatic hydrocarbons are hydrogenated until the number of aromatic rings becomes 1 or less on the average, when the polycyclic aromatic hydrocarbons are recycled to the cracking reforming reaction step, the hydrogenation reaction product can be easily converted to monocyclic aromatic hydrocarbons.
  • the content of polycyclic aromatic hydrocarbons in the hydrogenation reaction product obtainable in the hydrogenation reaction step is preferably adjusted to 20 mass% or less, and more preferably 10 mass% or less.
  • the content of polycyclic aromatic hydrocarbons in the hydrogenation reaction product is preferably smaller than the content of polycyclic aromatic hydrocarbons in the feedstock, and the content can be reduced as the amount of the hydrogenation catalyst is increased, and as the reaction pressure is increased.
  • the content of polycyclic aromatic hydrocarbons in the hydrogenation reaction product obtainable in the hydrogenation reaction step is preferably adjusted to 20 mass% or more.
  • hydrogen produced as a by-product in the cracking reforming reaction step can also be utilized. That is, hydrogen is collected in the hydrogenation collecting step that will be described below from the gas components obtained in the separation step, and in the hydrogen supply step, the collected hydrogen is supplied to the hydrogenation reaction step.
  • a fixed bed is suitably employed.
  • known hydrogenation catalysts for example, a nickel catalyst, a palladium catalyst, a nickel-molybdenum-based catalyst, a cobalt-molybdenum-based catalyst, a nickel-cobalt-molybdenum-based catalyst, and a nickel-tungsten-based catalyst
  • a nickel catalyst for example, a nickel catalyst, a palladium catalyst, a nickel-molybdenum-based catalyst, a cobalt-molybdenum-based catalyst, a nickel-cobalt-molybdenum-based catalyst, and a nickel-tungsten-based catalyst
  • the reaction temperature may vary depending on the hydrogenation catalyst used, but the reaction temperature is usually set to the range of 100°C to 450°C, more preferably 200°C to 400°C, and even more preferably 250°C to 380°C.
  • the reaction pressure may vary depending on the hydrogenation catalyst or feedstock used, but the reaction pressure is preferably set to the range of 0.7 MPa to 13 MPa, more preferably set to 1 MPa to 10 MPa, and particularly preferably set to 1 MPa to 7 MPa.
  • the reaction pressure is adjusted to 13 MPa or less, a hydrogenation reactor having a low durability pressure can be used, and the cost of equipment can be reduced.
  • reaction pressure is preferably 0.7 MPa or greater in view of the yield of the hydrogenation reaction.
  • the amount of hydrogen consumption is preferably 3000 scfb (506 Nm 3 /m 3 ) or less, more preferably 2500 scfb (422 Nm 3 /m 3 ) or less, and even more preferably 1500 scfb (253 Nm 3 /m 3 ) or less.
  • the amount of hydrogen consumption is preferably 300 scfb (50 Nm 3 /m 3 ) or greater in view of the yield of the hydrogenation reaction.
  • the liquid hourly space velocity is preferably set to from 0.1 h -1 to 20 h -1 , and more preferably set to from 0.2 h -1 to 10 h -1 .
  • LHSV liquid hourly space velocity
  • polycyclic aromatic hydrocarbons can be sufficiently hydrogenated at a lower hydrogenation reaction pressure.
  • LHSV is set to 0.1h -1 or higher, an excessive increase in the size of hydrogenation reactors can be avoided.
  • hydrogen is collected from the gas components obtained in the separation step.
  • the method for collecting hydrogen there are no particular limitations so long as hydrogen and other gases that are included in the gas components obtained in the separation step can be separated, and examples thereof include a pressure swing adsorption method (PSA method), a low temperature separation processing method, and a membrane separation method.
  • PSA method pressure swing adsorption method
  • a low temperature separation processing method low temperature separation processing method
  • a membrane separation method membrane separation method
  • the amount of hydrogen collected in the hydrogen collecting step is larger than the amount required for hydrogenating the heavy oil fraction or the light oil/kerosene fraction described above.
  • hydrogen obtained in the hydrogen collecting step is supplied to the hydrogenation reactor of the hydrogenation reaction step.
  • the amount of hydrogen supplied at that time is adjusted according to the amount of the remaining fraction obtained after naphthalene compounds have been separated in the naphthalene collecting step, which is supplied to the hydrogenation reaction step. Furthermore, if necessary, the hydrogen pressure is regulated.
  • the remaining fraction obtained after naphthalene compounds have been separated in the naphthalene collecting step described above can be hydrogenated by using the hydrogen produced as a by-product in the cracking reforming reaction step, and efficient operation of the apparatus can be promoted.
  • the hydrogenation reaction product is mixed with the feedstock, and the mixture is recycled to the cracking reforming reaction step.
  • the hydrogenation reaction product is a product obtained by allowing the remaining fraction obtained after naphthalene compounds have been separated in the naphthalene collecting step, to react in the hydrogenation reaction step.
  • LPG that is produced as a by-product in the cracking reforming reaction step is collected from the liquid fraction separated in the separation step.
  • a liquid fraction having 3 or 4 carbon numbers that is, propylene, propane, butene and butane are purified and collected as LPG.
  • the oil produced by the cracking reforming reaction in the method for producing aromatic hydrocarbons of the present embodiment unlike the products of hydrogenation cracking and the like in conventional petroleum purification processes, more of olefins such as propylene and butene are present. Therefore, if necessary, collection of olefins by hydrogenation or rectification can also be achieved.
  • monocyclic aromatic hydrocarbons having 6 to 8 carbon numbers can be produced with a relatively high yield from a feedstock containing polycyclic aromatic hydrocarbons, and as other chemical products, naphthalene compounds including naphthalene, or olefin compounds such as propylene, propane, butene and butane can also be produced.
  • naphthalene it has been conventional in general to produce naphthalene according to a crystallization method by which coal tar distillate oil is cooled, and thereby crystals are precipitated.
  • the crystallization method requires complicated steps, and there is a problem that the production cost is high.
  • the method for producing aromatic hydrocarbons of the present embodiment can obtain naphthalene with a relatively high purity, only by adding a naphthalene collecting step, or if necessary, a naphthalene compound separation and collection step to the process for producing monocyclic aromatic hydrocarbons having 6 to 8 carbon numbers. Therefore, in regard to the production cost for naphthalene (or naphthalene compounds), when the portion for producing monocyclic aromatic hydrocarbons having 6 to 8 carbon numbers is deducted, the production cost is markedly decreased as compared with conventional methods according to a crystallization method. Therefore, naphthalene (or naphthalene compounds) can be provided at low cost.
  • a hydrogenation reaction step of hydrogenating a portion of the liquid components separated in the separation process may be provided between the separation process and the purification and collection process.
  • the hydrogenation reaction product obtained in the hydrogenation reaction step may be distilled, and monocyclic aromatic hydrocarbons may be purified and collected.
  • a portion of the heavy oil fraction separated in the separation step may also be supplied to the hydrogenation reaction step without going through the naphthalene collecting step, and the portion may also be hydrogenated and recycled to the cracking reforming reaction process.
  • hydrogen obtained in a know hydrogen production method may be used instead of the hydrogen produced as a by-product in the cracking reforming reaction step, or hydrogen produced as a by-product in another contact cracking method may also be used.
  • the mixture thus obtained was vigorously stirred for 15 minutes in a mixer, and the gel was crushed to obtain a milky homogenously fine state.
  • this mixture was placed in an autoclave made of stainless steel, and a crystallization operation was carried out under self-pressure under the conditions of a temperature of 165°C, a time of 72 hours, and a stirring speed of 100 rpm.
  • the product was filtered to collect a solid product, and washing and filtration was repeated 5 times by using about 5 liters of deionized water.
  • the solid obtained by filtration was dried at 120°C, and the solid was calcined at 550°C for 3 hours under a stream of air.
  • the catalyst A further contains a silica binder (the content of the silica binder is 60 mass% relative to the total mass of the catalyst) in addition to the crystalline aluminosilicate, gallium and phosphorus.
  • the reaction product oil thus obtained was analyzed by an FID gas chromatographic method, and the amount of impurities between durene (boiling point: 196°C) and naphthalene (boiling point: 218°C) was 1.9 mass% relative to 100 of naphthalene. Furthermore, the amount of impurities between naphthalene and 2-methylnaphthalene (boiling point: 241°C) was 0.6 mass% relative to 100 of naphthalene, and 0.4 mass% relative to 100 of methylnaphthalene. Thus, it was found that there were very few components having a boiling point close to that of naphthalene.
  • reaction product oil thus obtained was fractionated in a rectifying column into a gas fraction, a fraction containing monocyclic aromatic hydrocarbons (benzene, toluene and xylene), and a heavy oil fraction having 9 or more carbon numbers (heavy oil fraction 1).
  • the heavy oil fraction 1 was further distilled in the rectifying column, and was fractionated into a fraction mainly containing naphthalene (boiling point: 218°C) and a fraction other than naphthalene (heavy oil fraction 2).
  • the yield of the monocyclic aromatic hydrocarbons (benzene, toluene, and crude xylene (xylene including a small amount of ethylbenzene and the like)) obtained by fractionation was 30 mass%, and the yield of the naphthalene fraction was 7 mass%. Meanwhile, the naphthalene purity in the naphthalene fraction was 96 mass%.
  • the reaction product oil thus obtained was analyzed by an FID gas chromatographic method, and the amount of impurities between durene (boiling point: 196°C) and naphthalene (boiling point: 218°C) was 2.4 mass% relative to 100 of naphthalene. Furthermore, the amount of impurities between naphthalene and 2-methylnaphthalene (boiling point: 241°C) was 1.6 mass% relative to 100 of naphthalene, and 0.9 mass% relative to 100 of methylnaphthalene. Thus, it was found that there were very few components having a boiling point close to that of naphthalene.
  • reaction product oil thus obtained was fractionated in a rectifying column into a gas fraction, a fraction containing monocyclic aromatic hydrocarbons (benzene, toluene and crude xylene), and a heavy oil fraction having 9 or more carbon numbers.
  • the heavy oil fraction having 9 or more carbon numbers was further distilled in the rectifying column, and was fractionated into a fraction mainly containing naphthalene (boiling point: 218°C) and a fraction other than naphthalene.
  • the yield of the monocyclic aromatic hydrocarbons (benzene, toluene, and crude xylene) obtained by fractionation was 37 mass%, and the yield of the naphthalene fraction was 9 mass%. Meanwhile, the naphthalene purity in the naphthalene fraction was 95 mass%.
  • the fraction other than naphthalene (heavy oil fraction 2: content of polycyclic aromatic hydrocarbons is 95 mass% or more) obtained in Example 1 was subjected to a hydrogenation reaction by using a commercially available nickel-molybdenum catalyst under the conditions of a reaction temperature of 350°C and a reaction pressure of 5 MPaG.
  • the hydrogenation reaction product thus obtained was 69 mass% of hydrocarbon compounds having one aromatic ring, and 28 mass% of compounds having two or more aromatic rings (polycyclic aromatic hydrocarbons).
  • the content of polycyclic aromatic hydrocarbons was reduced to a large extent.
  • a feedstock obtained by recycling the hydrogenation reaction product into the LCO indicated in Table 1 in an amount of 0.4 times the mass of LCO was brought into contact with the catalyst A (a catalyst produced by incorporating a silica binder to an MFI type zeolite supporting 0.4 mass% of gallium and 0.7 mass% of phosphorus, in an amount of 60 mass% relative to the total mass of the catalyst) in a fluidized bed reactor under the conditions of a reaction temperature of 550°C, a reaction pressure of 0.3 MPaG, and a contact time of 30 seconds, and was allowed to react therewith, and thus production of monocyclic aromatic hydrocarbons was carried out.
  • the catalyst A a catalyst produced by incorporating a silica binder to an MFI type zeolite supporting 0.4 mass% of gallium and 0.7 mass% of phosphorus, in an amount of 60 mass% relative to the total mass of the catalyst
  • the yield of monocyclic aromatic hydrocarbons (benzene, toluene and crude xylene) thus obtained was 36 mass%, and as compared with Example 1 in which the hydrogenation reaction product was not recycled, an increase in the yield of monocyclic aromatic hydrocarbons was observed.
  • naphthalene compounds including naphthalene can all be produced by using an oil containing polycyclic aromatic hydrocarbons such as LCO.

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Claims (9)

  1. Verfahren zum Erzeugen von aromatischen Kohlenwasserstoffen, wobei das Verfahren Folgendes umfasst:
    einen Schritt zum Durchführen einer Krack-Reformierungsreaktion durch Inberührungbringen eines Ausgangsmaterials mit einer 10 Vol.-%-Destillationstemperatur von wenigstens 140 °C und einer 90 Vol.-%-Destillationstemperatur von höchstens 380 °C, in einer Gasphase, mit einem Katalysator zum Erzeugen von monocyclischem aromatischem Kohlenwasserstoff, um zu bewirken, dass das Ausgangsmaterial mit dem Katalysator reagiert, und dadurch Erhalten eines Produkts, das monocyclische aromatische Kohlenwasserstoffe mit Kohlenstoffzahlen von 6 bis 8 und eine Schwerölfraktion mit einer Kohlenstoffzahl von wenigstens 9 beinhaltet;
    einen Schritt zum Trennen des Produkts durch entsprechendes Trennen von Gaskomponenten und einer Flüssigkeitsfraktion von dem Produkt, das von dem Krack-Reformierungsreaktionsschritt erhalten wurde, und danach Trennen der Flüssigkeitsfraktion in eine Flüssiggasfraktion, wobei eine Fraktion monocyclische aromatische Kohlenwasserstoffe mit Kohlenstoffzahlen von 6 bis 8 , und eine Schwerölfraktion mit einer Kohlenstoffzahl von wenigstens 9 beinhaltet;
    einen Schritt zum Aufreinigen der monocyclischen aromatischen Kohlenwasserstoffe mit Kohlenstoffzahlen von 6 bis 8 durch Trennen der Fraktion, die monocyclische aromatische Kohlenwasserstoffe mit Kohlenstoffzahlen von 6 bis 8 beinhaltet, in entsprechende Benzol-/Toluol-/Xylol-Komponenten, und danach Aufreinigen und Gewinnen der entsprechenden Benzol-/Toluol-/Xylol-Komponenten; und
    einen Schritt zum Gewinnen von Naphthalinverbindungen durch Trennen der Schwerölfraktion in eine Fraktion, die Naphthalinverbindungen beinhaltet, und eine Fraktion, die die Naphthalinverbindungen nicht beinhaltet, und danach Aufreinigen und Gewinnen der Naphthalinverbindungen,
    wobei in der Krack-Reformierungsreaktion in dem Ausgangsmaterial enthaltene polycyclische aromatische Kohlenwasserstoffe teilweise durch eine Wasserstoffübertragungsreaktion von gesättigten Kohlenwasserstoffen hydriert werden, indem die als eine Wasserstoffdonatorquelle in dem Ausgangsmaterial enthaltenen gesättigten Kohlenwasserstoffe verwendet werden, und die polycyclischen aromatischen Kohlenwasserstoffe durch Ringöffnung in monocyclische aromatische Kohlenwasserstoffe umgewandelt werden,
    wobei der Katalysator aus einem kristallinen Alumosilicat besteht oder der Katalysator ein kristallines Alumosilicat sowie Phosphor, Bor, Gallium und/oder Zink beinhaltet,
    wobei eine Reaktionstemperatur, die eingesetzt wird, wenn es dem Ausgangsmaterial ermöglicht wird, mit dem Katalysator zum Erzeugen von monocyclischem aromatischem Kohlenwasserstoff in der Krack-Reformierungsreaktion zu reagieren, von 400 °C bis 650 °C beträgt,
    wobei ein Reaktionsdruck, der eingesetzt wird, wenn es dem Ausgangsmaterial ermöglicht wird, mit dem Katalysator zum Erzeugen von monocyclischem aromatischem Kohlenwasserstoff in der Krack-Reformierungsreaktion zu reagieren, von 0,1 MPaG bis 1,5 MPaG beträgt, und
    wobei eine Berührungszeit, in der das Ausgangsmaterial mit dem Katalysator zum Herstellen von monocyclischem aromatischem Kohlenwasserstoff in der Krack-Reformierungsreaktion in Berührung gebracht wird, 5 Sekunden bis 150 Sekunden beträgt.
  2. Verfahren zum Erzeugen von aromatischen Kohlenwasserstoffen nach Anspruch 1, wobei der Katalysator ein kristallines Alumosilicat, Phosphor und/oder Bor und Gallium und/oder Zink beinhaltet.
  3. Verfahren zum Erzeugen von aromatischen Kohlenwasserstoffen nach Anspruch 1 oder 2, wobei im Schritt zum Gewinnen der Naphthalinverbindungen die Fraktion, die Naphthalinverbindungen beinhaltet, Methylnaphthalin und Dimethylnaphthalin sowie Naphthalin beinhaltet.
  4. Verfahren zum Erzeugen von aromatischen Kohlenwasserstoffen nach einem der Ansprüche 1 bis 3, ferner Folgendes umfassend:
    einen Schritt zum Hydrieren der verbleibenden Fraktion, die erhalten worden ist, nachdem Naphthalin in dem Naphthalingewinnungsschritt getrennt worden ist, und zum Erhalten eines Hydrierreaktionsprodukts; und
    einen Schritt zum Wiederverwerten des Hydrierreaktionsprodukts in der Krack-Reformierungsreaktion.
  5. Verfahren zum Erzeugen von aromatischen Kohlenwasserstoffen nach einem der Ansprüche 1 bis 4, wobei im Schritt zum Gewinnen von Naphthalinverbindungen eine Vorrichtung zum Trennen und Gewinnen von Naphthalinverbindungen eine Destilliervorrichtung ist.
  6. Verfahren zum Erzeugen von aromatischen Kohlenwasserstoffen nach einem der Ansprüche 1 bis 5, wobei das kristalline Alumosilicat einen Zeolith mit Poren von mittlerer Größe und/oder einen Zeolith mit Poren von großer Größe als Hauptkomponenten umfasst.
  7. Verfahren zum Erzeugen von aromatischen Kohlenwasserstoffen nach einem der Ansprüche 1 bis 6, wobei die Reaktionstemperatur, die eingesetzt wird, wenn es dem Ausgangsmaterial ermöglicht wird, mit dem Katalysator zum Erzeugen von monocyclischem aromatischem Kohlenwasserstoff in der Krack-Reformierungsreaktion zu reagieren, von 450 °C bis 650 °C beträgt.
  8. Verfahren zum Erzeugen von aromatischen Kohlenwasserstoffen nach einem der Ansprüche 1 bis 7, wobei eine Menge von Phosphor und/oder Bor im Katalysator 0,1 Massen-% bis 10 Massen-% bezogen auf das Gesamtgewicht des Katalysators beträgt.
  9. Verfahren zum Erzeugen von aromatischen Kohlenwasserstoffen nach einem der Ansprüche 1 bis 8, wobei eine Menge von Gallium und/oder Zink im Katalysator 0,01 Massen-% bis 5,0 Massen-% bezogen auf das Gesamtgewicht des Katalysators beträgt.
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CN103097323B (zh) 2015-07-08
EP2617697A1 (de) 2013-07-24
EP2617697A4 (de) 2014-06-04
WO2012036182A1 (ja) 2012-03-22
JP2012062255A (ja) 2012-03-29
CN103097323A (zh) 2013-05-08
JP5485088B2 (ja) 2014-05-07
US20130184506A1 (en) 2013-07-18
KR20130108319A (ko) 2013-10-02

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