WO2012161019A1 - Composition d'huile lourde c et son procédé de fabrication - Google Patents

Composition d'huile lourde c et son procédé de fabrication Download PDF

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Publication number
WO2012161019A1
WO2012161019A1 PCT/JP2012/062312 JP2012062312W WO2012161019A1 WO 2012161019 A1 WO2012161019 A1 WO 2012161019A1 JP 2012062312 W JP2012062312 W JP 2012062312W WO 2012161019 A1 WO2012161019 A1 WO 2012161019A1
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WIPO (PCT)
Prior art keywords
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heavy oil
oil composition
mass
cracking
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Ceased
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PCT/JP2012/062312
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English (en)
Japanese (ja)
Inventor
裕太 三ツ井
勝彦 土師
泰之 岩佐
柳川　真一朗
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Eneos Corp
Original Assignee
JX Nippon Oil and Energy Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by JX Nippon Oil and Energy Corp filed Critical JX Nippon Oil and Energy Corp
Priority to US14/117,241 priority Critical patent/US20140073821A1/en
Priority to CN201280025267.5A priority patent/CN103562357B/zh
Priority to EP12789718.9A priority patent/EP2716741A4/fr
Publication of WO2012161019A1 publication Critical patent/WO2012161019A1/fr
Anticipated expiration legal-status Critical
Ceased legal-status Critical Current

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Classifications

    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of 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
    • 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
    • C10L—FUELS NOT OTHERWISE PROVIDED FOR; NATURAL GAS; SYNTHETIC NATURAL GAS OBTAINED BY PROCESSES NOT COVERED BY SUBCLASSES C10G OR C10K; LIQUIFIED PETROLEUM GAS; USE OF ADDITIVES TO FUELS OR FIRES; FIRE-LIGHTERS
    • C10L1/00—Liquid carbonaceous fuels
    • C10L1/04—Liquid carbonaceous fuels essentially based on blends of hydrocarbons
    • C10L1/08—Liquid carbonaceous fuels essentially based on blends of hydrocarbons for compression ignition
    • 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
    • C10G2300/1096—Aromatics or polyaromatics
    • 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
    • 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
    • C10G2300/304—Pour point, cloud point, cold flow properties
    • 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
    • C10G2300/308—Gravity, density, e.g. API

Definitions

  • the present invention relates to a C heavy oil composition and a method for producing the same, and more particularly to a C heavy oil composition used as a fuel for a combustion device such as a boiler, a diesel device, a gas turbine, or a ship.
  • a combustion device such as a boiler, a diesel device, a gas turbine, or a ship.
  • C heavy oil is widely used as fuel for external combustion equipment such as boilers, diesel engine equipment fuel for large ships and power generation, gas turbine equipment fuel, and the like.
  • marine C heavy oils are sometimes loaded in other countries and the like, and engine troubles due to combustion failures often occur, which is a big problem.
  • produce a combustion failure is increasing (refer nonpatent literature 1).
  • Patent Document 1 Japanese Patent Laid-Open No. Hei 8-277396 discloses that heavy oil is treated with water and a specific nonionic surfactant to form an oil-in-water type heavy oil.
  • Patent Document 2 Japanese Patent Laid-Open No. 2003-964764 discloses a method for improving combustibility by containing 50% or more of catalytically cracked light diesel oil (LCO) and defining a cetane index. Yes.
  • LCO catalytically cracked light diesel oil
  • the quality of marine fuel oil has been remarkably lowered, and sludge generation, ignitability, and combustibility have been reduced. For this reason, combustion failures frequently occur in large diesel engines that are installed, causing smoke, rising exhaust temperature, exhaust system contamination, abnormal wear of cylinders, rings, etc., all of which are realistic. It does not indicate a solution.
  • the present invention has been made in view of such circumstances, and it is difficult to generate sludge, has excellent ignition performance and combustion performance, and stably operates combustion equipment such as external combustion equipment, diesel equipment, and gas turbine equipment. It is an object of the present invention to provide a C heavy oil composition that can be used and a method for producing the same.
  • the present inventors have found that the above problems can be solved by combining specific substrates, and have completed the present invention. That is, the present invention is as follows.
  • a decomposition modified base material having a total aromatic content of 80% by volume or more and a density at 15 ° C. of 0.90 to 1.20 g / cm 3 is blended by 1% to 45% by volume based on the total amount of the composition.
  • the 10% by volume distillation temperature (T10) of the cracked and modified base material is 130 to 270 ° C.
  • the 50% by volume distillation temperature (T50) is 190 to 290 ° C.
  • the 90% by volume distillation temperature (T90) is The method for producing a C heavy oil composition according to the above [1] or [2], wherein the temperature is 230 to 390 ° C.
  • the cracking and reforming base material contains medium pore zeolite and / or large pore zeolite as a feedstock having a 10 vol% distillation temperature of 140 ° C or higher and a 90 vol% distillation temperature of 380 ° C or lower. It is produced by contacting with a catalyst for cracking and reforming reaction, and performing a cracking and reforming reaction at a reaction temperature of 400 to 650 ° C., a reaction pressure of 1.5 MPaG or less, and a contact time of 1 to 300 seconds.
  • a method for producing a C heavy oil composition according to any one of [3] to [3].
  • the density at 15 ° C. obtained by the method for producing a C heavy oil composition according to any one of [1] to [4] is 0.85 to 1.05 g / cm 3 , and the kinematic viscosity at 50 ° C. C heavy oil composition having 400 mm 2 / s or less, sulfur content of 3.5% by mass or less, nitrogen content of 1% by mass or less, and flash point of 70 ° C. or more.
  • the C heavy oil composition of the present invention hardly generates sludge and has excellent ignitability and combustibility. Therefore, the C heavy oil composition of the present invention is very useful as fuel for external combustion equipment fuel such as boilers, diesel engine equipment fuel for large ships and power generation, and gas turbine equipment fuel.
  • the method for producing a C heavy oil composition of the present invention comprises a C heavy oil containing a cracked and modified base material having a total aromatic content of 80% by volume or more and a density at 15 ° C. of 0.90 to 1.20 g / cm 3. 1 vol% or more and 45 vol% or less are blended based on the total amount of the composition.
  • the lower limit of the blending amount of the cracked modified base material is required to be 1% by volume or more based on the total amount of C heavy oil composition, preferably 5% by volume or more, more preferably 10% by volume or more, and 15% by volume or more. Further preferred.
  • the upper limit of the blending amount of the degradation-modified base material needs to be 45% by volume or less, preferably 40% by volume or less, and more preferably 35% by volume or less.
  • the total aromatic content of the cracked and modified base material blended in the C heavy oil composition of the present invention is required to be 80% by volume or more from the viewpoint of ensuring compatibility as a cutback material, and 90% by volume or more. Preferably there is.
  • the total aromatic content means the content of the total aromatic content measured by the Petroleum Institute method JPI-5S-49-97 “Petroleum products—Hydrocarbon type test method—High performance liquid chromatograph method”. .
  • Density at 15 °C decomposition modified substrate to be blended into fuel oil C compositions of the present invention is required to be 0.90 g / cm 3 or more 1.20 g / cm 3 or less.
  • the density at 15 ° C. means a value obtained in accordance with JIS K2249 “Crude oil and petroleum products—density test method and density / mass / capacity conversion table”.
  • the properties other than the total aromatic content and the density at 15 ° C. of the cracked and modified base material blended in the C heavy oil composition of the present invention are not particularly limited, but preferably have the following properties.
  • the kinematic viscosity at 50 ° C. of the degradation-modified base material blended in the C heavy oil composition of the present invention is preferably 0.3 mm 2 / s to 10 mm 2 / s.
  • the upper limit of the kinematic viscosity at 50 ° C. is more preferably 8 mm 2 / s or less, and further preferably 6 mm 2 / s or less.
  • the sulfur content (sulfur content) of the cracked and modified base material blended in the C heavy oil composition of the present invention is preferably 8000 mass ppm or less, and is 5000 mass ppm or less from the viewpoint of reducing sulfur compounds in the combustion exhaust gas. More preferred is 4000 ppm by mass or less.
  • the nitrogen content (nitrogen content) of the cracked and modified base material blended in the C heavy oil composition of the present invention is preferably 100 ppm by mass or less, and from the viewpoint of reducing nitrogen compounds in the combustion exhaust gas, 80 ppm by mass or less is preferable. More preferred is 70 mass ppm or less.
  • the distillation property of the cracked and modified base material blended in the C heavy oil composition of the present invention has an initial boiling point (IBP) of preferably 105 ° C. or higher and 250 ° C. or lower, more preferably 120 ° C. or higher and 240 ° C. or lower, and 10% by volume distillation.
  • the outlet temperature (T10) is preferably 130 ° C. or higher and 270 ° C. or lower, more preferably 150 ° C. or higher and 250 ° C. or lower
  • the 50 vol% distillation temperature (T50) is preferably 190 ° C. or higher and 290 ° C. or lower, more preferably 210 ° C. or higher. 270 ° C.
  • T90 90% by volume distillation temperature
  • EP end point
  • the kinematic viscosity at 50 ° C. is a value obtained according to JIS K2283 “Crude oil and petroleum products—Kinematic viscosity test method and viscosity index calculation method”, and the sulfur content is defined in JIS K2541-1992.
  • the nitrogen content measured in conformity with the distillation property means that measured in accordance with JIS K2254 "Petroleum products-Distillation test method-Atmospheric pressure method”.
  • the cracking and reforming base material according to the present invention contains medium pore zeolite and / or large pore zeolite as a feed oil having a 10 vol% distillation temperature of 140 ° C or higher and a 90 vol% distillation temperature of 380 ° C or lower. It is produced by contacting with a catalyst for cracking and reforming reaction, and performing a cracking and reforming reaction at a reaction temperature of 400 to 650 ° C., a reaction pressure of 1.5 MPaG or less, and a contact time of 1 to 300 seconds.
  • the cracking / reforming substrate used in the present invention is produced by fractional distillation from the cracking / reforming reaction product obtained by the following cracking / reforming reaction.
  • the feedstock oil is brought into contact with the catalyst for cracking and reforming reaction, the saturated hydrocarbon contained in the feedstock oil is used as a hydrogen donor source, and polycyclic aromatic hydrocarbons are converted by hydrogen transfer reaction from the saturated hydrocarbon.
  • polycyclic aromatic hydrocarbons are converted by hydrogen transfer reaction from the saturated hydrocarbon.
  • the fuel base material mainly containing aromatic hydrocarbons can be produced.
  • the feed oil for the cracking and reforming reaction is preferably an oil having a 10 vol% distillation temperature of 140 ° C or higher and a 90 vol% distillation temperature of 380 ° C or lower, and the 10 vol% distillation temperature of the raw oil is 150 ° C or higher. More preferably, the 90 vol% distillation temperature of the feedstock is more preferably 360 ° C or lower.
  • the 10 vol% distillation temperature and 90 vol% distillation temperature mentioned here mean values measured in accordance with JIS K2254 “Petroleum products-distillation test method”. Examples of the feed oil having a 10% by volume distillation temperature of 140 ° C. or higher and a 90% by volume distillation temperature of 380 ° C.
  • LCO cracked light oil
  • Examples include coal liquefied oil, heavy oil hydrocracked refined oil, straight-run kerosene, straight-run light oil, coker kerosene, coker light oil, and oil sand hydrocracked refined oil.
  • a fixed bed, a moving bed, a fluidized bed and the like can be mentioned.
  • a fluidized bed capable of continuously removing the coke component adhering to the catalyst and performing the reaction stably is preferable, and the space between the reactor and the regenerator is preferable.
  • a continuous regenerative fluidized bed in which the catalyst circulates and allows continuous reaction-regeneration is particularly preferred.
  • the feedstock oil in contact with the cracking reforming reaction catalyst is preferably in a gas phase. Moreover, you may dilute a raw material with gas as needed.
  • the catalyst for the cracking reforming reaction contains crystalline aluminosilicate.
  • the crystalline aluminosilicate is preferably a medium pore zeolite and / or a large pore zeolite because the yield of monocyclic aromatic hydrocarbons can be further increased.
  • the medium pore zeolite is a zeolite having a 10-membered ring skeleton structure. Examples of the medium pore zeolite include AEL type, EUO type, FER type, HEU type, MEL type, MFI type, NES type, and TON type. And zeolite having a WEI type crystal structure. Among these, the MFI type is preferable because the yield of monocyclic aromatic hydrocarbons can be further increased.
  • the large pore zeolite is a zeolite having a 12-membered ring skeleton structure.
  • Examples of the large pore zeolite include AFI type, ATO type, BEA type, CON type, FAU type, GME type, LTL type, and MOR type. , Zeolites of MTW type and OFF type crystal structures.
  • BEA type, FAU type, and MOR type are preferable in terms of industrial use, and the BEA type is more preferable because the yield of monocyclic aromatic hydrocarbons can be further increased.
  • the crystalline aluminosilicate may contain, in addition to the medium pore zeolite and the large pore zeolite, a small pore zeolite having a skeleton structure having a 10-membered ring or less, and a very large pore zeolite having a skeleton structure having a 14-membered ring or more.
  • examples of the small pore zeolite include zeolites having crystal structures of ANA type, CHA type, ERI type, GIS type, KFI type, LTA type, NAT type, PAU type, and YUG type.
  • Examples of the ultra-large pore zeolite include zeolites having CLO type and VPI type crystal structures.
  • the content of the crystalline aluminosilicate in the cracking and reforming reaction catalyst is 60 to 100% by weight when the entire catalyst for cracking and reforming reaction is 100% by weight. Preferably, 70 to 100% by mass is more preferable, and 90 to 100% by mass is particularly preferable. If the content of the crystalline aluminosilicate is 60% by mass or more, the yield of monocyclic aromatic hydrocarbons can be sufficiently increased.
  • the content of crystalline aluminosilicate in the cracking and reforming reaction catalyst is 20 to 60% by weight when the entire catalyst for cracking and reforming reaction is 100% by weight.
  • the content of the crystalline aluminosilicate is 20% by mass or more, the yield of monocyclic aromatic hydrocarbons can be sufficiently increased.
  • the content of the crystalline aluminosilicate exceeds 60% by mass, the content of the binder that can be blended with the catalyst is reduced, which may be unsuitable for fluidized beds.
  • the catalyst for decomposition reforming reaction preferably contains phosphorus and / or boron.
  • the catalyst for cracking and reforming reaction contains phosphorus and / or boron, it is possible to prevent the yield of monocyclic aromatic hydrocarbons from decreasing with time and to suppress the formation of coke on the catalyst surface.
  • Examples of the method for incorporating phosphorus into the cracking reforming reaction catalyst include an ion exchange method and an impregnation method. Specifically, a method in which phosphorus is supported on crystalline aluminosilicate, crystalline aluminogallosilicate, or crystalline aluminodine silicate, a phosphorus compound is included during zeolite synthesis, and a part of the crystalline aluminosilicate skeleton is added to phosphorus. Examples include a replacement method, a method using a crystal accelerator containing phosphorus during zeolite synthesis, and the like.
  • the phosphate ion-containing aqueous solution used at that time is not particularly limited, but was prepared by dissolving phosphoric acid, diammonium hydrogen phosphate, ammonium dihydrogen phosphate, and other water-soluble phosphates in water at an arbitrary concentration. Can be preferably used.
  • Examples of the method for incorporating boron into the cracking reforming reaction catalyst include an ion exchange method and an impregnation method. Specifically, a method in which boron is supported on crystalline aluminosilicate, crystalline aluminogallosilicate, or crystalline aluminodine silicate, a boron compound is included during zeolite synthesis, and a part of the skeleton of crystalline aluminosilicate is combined with boron. Examples include a replacement method, a method using a crystal accelerator containing boron at the time of zeolite synthesis, and the like.
  • the phosphorus and / or boron content in the cracking reforming reaction catalyst is preferably 0.1 to 10% by mass relative to the total weight of the catalyst, and more preferably the lower limit is 0.5% by mass or more.
  • the upper limit is more preferably 9% by mass or less, and particularly preferably 8% by mass or less.
  • the cracking and reforming reaction catalyst may contain gallium and / or zinc as necessary. If gallium and / or zinc is contained, the production rate of monocyclic aromatic hydrocarbons can be increased.
  • the gallium-containing form in the catalyst for cracking and reforming reaction includes those in which gallium is incorporated in the lattice skeleton of crystalline aluminosilicate (crystalline aluminogallosilicate), and those in which gallium is supported on crystalline aluminosilicate (gallium) Supported crystalline aluminosilicate) and those containing both.
  • Zinc-containing forms in the catalyst for cracking and reforming reaction include those in which zinc is incorporated in the lattice skeleton of crystalline aluminosilicate (crystalline aluminodin silicate), and in which zinc is supported on crystalline aluminosilicate (zinc Supported crystalline aluminosilicate) and those containing both.
  • Crystalline aluminogallosilicate and crystalline aluminodine silicate have a structure in which SiO 4 , AlO 4 and GaO 4 / ZnO 4 structures are present in the skeleton.
  • the crystalline aluminogallosilicate and the crystalline aluminodine silicate can be obtained by, for example, gel crystallization by hydrothermal synthesis, or a method of inserting gallium or zinc into the lattice skeleton of the crystalline aluminosilicate.
  • Crystalline aluminogallosilicate and crystalline aluminozine silicate can be obtained by a method of inserting aluminum into the lattice skeleton of crystalline gallosilicate or crystalline zincosilicate.
  • the gallium-supporting crystalline aluminosilicate is obtained by supporting gallium on a crystalline aluminosilicate by a known method such as an ion exchange method or an impregnation method.
  • the gallium source used in this case is not particularly limited, and examples thereof include gallium salts such as gallium nitrate and gallium chloride, and gallium oxide.
  • the zinc-supporting crystalline aluminosilicate is obtained by supporting zinc on a crystalline aluminosilicate by a known method such as an ion exchange method or an impregnation method. Although it does not specifically limit as a zinc source used in that case, Zinc salts, such as zinc nitrate and zinc chloride, zinc oxide, etc. are mentioned.
  • the content of gallium and / or zinc in the cracking reforming reaction catalyst is 0.01-5.
  • the content is preferably 0% by mass, and more preferably 0.05 to 2.0% by mass. If the content of gallium and zinc is 0.01% by mass or more, the production rate of monocyclic aromatic hydrocarbons can be increased, and if it is 5.0% by mass or less, the yield of monocyclic aromatic hydrocarbons Can be higher.
  • the catalyst for cracking and reforming reaction is made into, for example, a powder form, a granular form, a pellet form or the like according to the reaction format.
  • a fluidized bed it is in the form of powder, and in the case of a fixed bed, it is in the form of particles or pellets.
  • the average particle size of the catalyst used in the fluidized bed is preferably 30 to 180 ⁇ m, more preferably 50 to 100 ⁇ m.
  • the bulk density of the catalyst used in the fluidized bed is preferably 0.4 to 1.8 g / cc, more preferably 0.5 to 1.0 g / cc.
  • the average particle size represents a particle size of 50% by mass in the particle size distribution obtained by classification with a sieve, and the bulk density is a value measured by the method of JIS standard R9301-2-3.
  • an inert oxide may be blended into the catalyst as a binder and then molded using various molding machines.
  • the cracking reforming reaction catalyst contains an inorganic oxide such as a binder, a binder containing phosphorus may be used.
  • the reaction temperature when the raw material oil is brought into contact with and reacted with the cracking reforming reaction catalyst is not particularly limited, but is preferably 400 to 650 ° C. If the minimum of reaction temperature is 400 degreeC or more, raw material oil can be made to react easily, More preferably, it is 450 degreeC or more. Moreover, if the upper limit of reaction temperature is 650 degrees C or less, the yield of monocyclic aromatic hydrocarbon can be made high enough, More preferably, it is 600 degrees C or less.
  • the reaction pressure when the raw material oil is brought into contact with and reacted with the cracking reforming reaction catalyst is preferably 1.5 MPaG or less, more preferably 1.0 MPaG or less. If the reaction pressure is 1.5 MPaG or less, the by-product of light gas can be suppressed and the pressure resistance of the reactor can be lowered.
  • the contact time between the feedstock and the cracking reforming reaction catalyst is not particularly limited as long as the desired reaction proceeds substantially.
  • the gas passage time on the cracking reforming reaction catalyst is 1 to 300 seconds.
  • the lower limit is more preferably 5 seconds or more
  • the upper limit is more preferably 150 seconds or less. If the contact time is 1 second or longer, the reaction can be performed reliably, and if the contact time is 300 seconds or shorter, accumulation of carbonaceous matter in the catalyst due to coking or the like can be suppressed. Or the generation amount of the light gas by decomposition
  • the cracking and reforming substrate according to the present invention can be produced.
  • a known distillation apparatus or gas-liquid separation apparatus can be used.
  • a distillation apparatus what can distill and isolate
  • the cracking and reforming base material according to the present invention is preferably a fraction mainly containing a hydrocarbon having 9 or more carbon atoms.
  • the C heavy oil base material to be blended in addition to the cracking modified base material is not particularly limited, but is atmospheric distillation light oil, atmospheric distillation residual oil, residual desulfurized gas oil, vacuum distillation.
  • Light oil, vacuum distillation residual oil, extract oil, catalytic cracking light oil, catalytic cracking residual oil and the like can be mentioned.
  • these C heavy oil base materials can be used singly or in combination of two or more for the cracking modified base material.
  • atmospheric distillation light oil and atmospheric distillation residual oil are light oil and residual oil obtained by distilling crude oil at atmospheric pressure with an atmospheric distillation apparatus.
  • the residual oil desulfurized light oil is a light oil obtained when depressurizing normal pressure residual oil or reduced pressure residual oil in a residual oil desulfurization apparatus.
  • a vacuum distillation light oil and a vacuum distillation residual oil are a light oil and a residual oil obtained by distilling a normal pressure residual oil under reduced pressure with a vacuum distillation apparatus.
  • Extract oil is an aromatic component that is not suitable for lubricating oil among the fractions extracted from the vacuum distillation apparatus for lubricating oil raw material by solvent extraction.
  • the catalytic cracking light oil and the catalytic cracking residual oil are a light oil and a residual oil obtained by cracking a vacuum distillation light oil, a vacuum distillation residual oil and the like in a fluid catalytic cracking apparatus.
  • the blending ratio of the C heavy oil base is 55 to 99% by volume, preferably 60 to 95% by volume, and 65 to 90% by volume based on the total amount of the C heavy oil composition. % Is more preferable, and 65 to 85% by volume is most preferable.
  • the C heavy oil composition according to the present invention needs to be a C heavy oil composition that satisfies the JIS class 3 heavy oil standard obtained by using the above-described decomposition modified base material as an essential component.
  • a C heavy oil composition having a bicyclic aromatic hydrocarbon content of 10 volume% to 45 volume% is produced.
  • the lower limit of the bicyclic aromatic hydrocarbon content is preferably 10% by volume or more for ensuring compatibility and suppressing sludge formation, and the upper limit is preferably 45% by volume or less for ensuring combustibility.
  • the content of the bicyclic aromatic hydrocarbon means the aromatic fraction fractionated by the Petroleum Institute method JPI-5S-22-83 “Asphalt composition analysis method by column chromatography”. Means the bicyclic aromatic hydrocarbon content measured by the method JPI-5S-49-97 “Petroleum products—Hydrocarbon type test method—High performance liquid chromatograph method”.
  • the properties other than the bicyclic aromatic hydrocarbon content of the C heavy oil composition according to the present invention are not particularly limited, but preferably have the following properties.
  • the C heavy oil composition according to the present invention has a 15 ° C. density (density at 15 ° C.) of preferably 0.85 g / cm 3 or more, more preferably 0.88 g / cm 3 or more, and 0.90 g / cm 3. Most preferably, it is cm 3 or more. Further, it is preferably 1.05 g / cm 3 or less, more preferably 1.00 g / cm 3 or less, and most preferably 0.99 g / cm 3 or less. When the density at 15 ° C. is less than 0.85 g / cm 3, the calorific value per capacity is small, which is not preferable. When the density is higher than 1.05 g / cm 3, combustion failure is likely to occur.
  • the 70 ° C. density density at 15 ° C.
  • the density (density at 70 ° C.) of the C heavy oil composition according to the present invention is preferably 0.80 g / cm 3 or more, and more preferably 0.83 g / cm 3 or more. Further, it is preferably 1.00 g / cm 3 or less, more preferably 0.95 g / cm 3 or less.
  • the density at 70 ° C. is less than 0.80 g / cm 3
  • the calorific value per capacity is small, which is not preferable.
  • the density is higher than 1.00 g / cm 3 , combustion failure tends to occur, which is not preferable.
  • the density means a value obtained in accordance with JIS K2249 “Crude oil and petroleum products—density test method and density / mass / capacity conversion table”.
  • the kinematic viscosity at 50 ° C. of the C heavy oil composition according to the present invention is preferably 400 mm 2 / s or less, more preferably 350 mm 2 / s or less, and most preferably 300 mm 2 / s or less.
  • the kinematic viscosity at 100 ° C. of the C heavy oil composition according to the present invention is preferably 50 mm 2 / s or less, and more preferably 45 mm 2 / s or less.
  • the kinematic viscosity means a value obtained in accordance with JIS K2283 “Crude oil and petroleum products—Kinematic viscosity test method and viscosity index calculation method”.
  • the sulfur content of the C heavy oil composition according to the present invention is preferably 3.5% by mass or less, and more preferably 3.0% by mass or less. When there is more sulfur content than 3.5 mass%, there exists a possibility that the sulfur oxide discharged
  • the sulfur content means a residual carbon content measured by JIS K2541 “Crude oil and petroleum products—Sulfur content test method”.
  • the nitrogen content of the C heavy oil composition according to the present invention is preferably 1.0% by mass or less, and more preferably 0.5% by mass or less.
  • the nitrogen content means a residual carbon content measured by JIS K2609 “Crude oil and petroleum products—nitrogen content test method”.
  • the flash point of the C heavy oil composition according to the present invention is preferably 70 ° C or higher, more preferably 72 ° C or higher, from the viewpoint of safety in handling.
  • the flash point as used in the present invention means a value measured by the Penschramten sealed type of JIS K2265 “Crude oil and petroleum products—Flash point test method”.
  • the CCAI of the C heavy oil composition according to the present invention is preferably 900 or less, and more preferably 870 or less. When CCAI is higher than 900, combustion failure is likely to occur.
  • CCAI Calculated Carbon Aromaticity Index: based on the decision of the International Combustion Engine Conference
  • the residual carbon content of the C heavy oil composition according to the present invention is preferably 15% by mass or less, and more preferably 10% by mass or less. When the residual carbon content is more than 15% by mass, combustion failure is likely to occur.
  • the residual carbon content means a residual carbon content measured by JIS K2270 “Crude oil and petroleum products—residual carbon content test method”.
  • the ash content of the C heavy oil composition according to the present invention is preferably 0.10% by mass or less, and more preferably 0.05% by mass or less. When the ash content is more than 0.10% by mass, combustion trouble is likely to occur.
  • ash means a value obtained in accordance with JIS K2272 “Testing method for ash and sulfated ash of crude oil and petroleum products”.
  • the vanadium content of the C heavy oil composition according to the present invention is preferably 100 mass ppm or less, and more preferably 80 mass ppm or less. When the content of vanadium is more than 100 mass ppm, combustion failure is likely to occur.
  • vanadium and content mean values obtained according to JPI-5S-11 “Testing method for vanadium content in heavy oil”.
  • the water content of the C heavy oil composition according to the present invention is preferably 0.5% by volume or less, and more preferably 0.3% by volume or less. If the water content is more than 0.5% by volume, it will precipitate as ice in the winter season, which tends to cause metal corrosion and filter clogging.
  • the moisture in the present invention means a value measured by JIS K2275 “Crude oil and petroleum products—moisture test method”.
  • the ignition delay of the C heavy oil composition according to the present invention measured by a fuel ignition tester is preferably 15 ms or less.
  • the ignition delay measured by the fuel ignitability tester may be 15 ms or less.
  • it is 13 ms or less, more preferably 11 ms or less.
  • the combustion time of the C heavy oil composition according to the present invention as measured by a fuel ignitability tester is preferably 25 ms or less. In order to stably operate the diesel engine equipment, it is effective that the flame length in the combustion chamber is short. Therefore, the combustion time measured by the fuel ignitability tester is preferably 25 ms or less, more preferably 23 ms or less.
  • the fuel ignitability tester is “Fuel Ignition Analyzer: FIA-100” manufactured by Fuel Tech Co., Ltd., which is placed in a constant volume combustion chamber filled with air having a volume of 1 L, a pressure of 4.5 MPa, and a temperature of 450 ° C. About 0.1 ml of fuel heated to 120 ° C. is injected at an injection pressure of 20 MPa, and the ignition delay time and combustion time are measured from the pressure change in the combustion chamber.
  • the ignition delay is the time when the pressure in the combustion chamber rises by 0.02 MPa from the initial pressure.
  • the combustion time is a time obtained by subtracting the ignition delay time from the maximum pressure attainment time.
  • thermogravimetric-differential thermal analysis means that a sample is heated at a predetermined temperature condition, and the weight loss associated with vaporization / pyrolysis, etc. and the change in heat quantity associated with vaporization / oxidation / thermal decomposition, etc. are simultaneously measured. It is an analysis method.
  • a sample is weighed on a platinum pan having an inner diameter of 5 mm, and set in a Thermoflex TAS300 manufactured by RIGAKU. Next, the sample is heated from room temperature to 1000 ° C. at 100 ° C./min.
  • the 50% weight loss temperature in a nitrogen atmosphere (100 ml / min) by thermogravimetric-differential thermal analysis of the C heavy oil composition according to the present invention is preferably 600 ° C. or less, more preferably 550 ° C. or less. .
  • the 50% weight loss temperature in a nitrogen atmosphere by thermogravimetric-differential thermal analysis is higher than 600 ° C., combustion failure tends to occur.
  • the 90% weight loss temperature in a nitrogen atmosphere (100 ml / min) by thermogravimetric-differential thermal analysis of the C heavy oil composition according to the present invention is preferably 800 ° C. or less, more preferably 750 ° C. or less. . If the 90% weight loss temperature in a nitrogen atmosphere by thermogravimetric-differential thermal analysis is higher than 800 ° C., combustion failure is likely to occur.
  • the C heavy oil composition according to the present invention comprises a low temperature fluidity improver, a cetane number improver, an antioxidant, a stabilizer, a dispersant, a metal deactivator, a microbial disinfectant, a combustion aid, a charge as necessary.
  • Various additives such as an inhibitor, a discriminating agent, and a coloring agent can also be contained.
  • the additive currently marketed may have diluted the active ingredient which contributes to the effect which the additive aimed at with the appropriate solvent.
  • the addition amount is arbitrary, but is usually 0.5% by mass or less, preferably 0.2% by mass or less, based on the total amount of C heavy oil composition.
  • Examples and Comparative Examples The test fuels of Examples 1 to 4 were the cracked and reformed base materials shown in Table 1, and the vacuum distillation residue obtained by distilling the atmospheric residue with a vacuum distillation apparatus under reduced pressure, and the crude oil with the atmospheric distillation apparatus. A straight-run gas oil obtained by distillation at normal pressure was used for adjustment. As a comparison, a sample with no decomposition-modified base material and a commercial product were prepared. In addition, the decomposition modification base material shown in Table 1 was manufactured with the following method.
  • Fluid catalytic cracking light oil LCO (10 vol% distillation temperature is 215 ° C, 90 vol% distillation temperature is 318 ° C, density at 15 ° C is 0.9258 g / cm 3 , saturation is 23 vol%, olefin content is 2 vol %, Total aromatic content is 75 vol%), reaction temperature: 538 ° C., reaction pressure: 0.3 MPaG, contact time between LCO and catalyst is 60 seconds in a fluidized bed reactor.
  • the catalyst was brought into contact with and reacted with a catalyst for use (MFI type zeolite carrying 0.2% by mass of gallium and 0.7% by mass of phosphorus and containing a binder) to carry out a decomposition and reforming reaction.
  • a catalyst for use MFI type zeolite carrying 0.2% by mass of gallium and 0.7% by mass of phosphorus and containing a binder
  • the cracking and reforming reaction product was fractionated to produce cracking and reforming substrates 1 to 3 shown in Table 1.
  • the C heavy oil composition according to the present invention hardly generates sludge and has excellent ignitability and combustibility.
  • Fuel for external combustion equipment such as boilers, diesel engine equipment fuel for large ships and power generation, and gas turbine equipment fuel It is very useful as a fuel.

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  • Chemical & Material Sciences (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Engineering & Computer Science (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • General Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)

Abstract

L'invention concerne un procédé de fabrication d'une composition d'huile lourde C qui ne génère guère de boue, présente une excellente performance d'allumage et une excellente performance de combustion, et qui permet le fonctionnement stable d'un dispositif de combustion tel qu'un dispositif de combustion externe, un dispositif diesel et un dispositif de turbine à gaz. Le procédé selon l'invention est un procédé de fabrication d'une composition d'huile lourde C ayant une teneur en hydrocarbures aromatiques bicycliques de 10 à 45 % en volume, bornes comprises, qui est caractérisé par l'incorporation par mélange d'une matière de base décomposée/reformée ayant une teneur totale en composants aromatiques de 80 % en volume ou plus et une masse volumique de 0,90-1,20 g/cm3 à 15 °C dans une quantité de 1 à 45 % en volume, bornes comprises, par rapport à la quantité totale de la composition.
PCT/JP2012/062312 2011-05-26 2012-05-14 Composition d'huile lourde c et son procédé de fabrication Ceased WO2012161019A1 (fr)

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EP12789718.9A EP2716741A4 (fr) 2011-05-26 2012-05-14 Composition d'huile lourde c et son procédé de fabrication

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JP5847673B2 (ja) * 2012-09-07 2016-01-27 Ｊｘ日鉱日石エネルギー株式会社 Ｃ重油組成物
CN104745250A (zh) * 2013-12-27 2015-07-01 永港伟方（北京）科技股份有限公司 一种重油节能环保添加剂及其制备方法和应用
JP6373530B1 (ja) * 2016-12-01 2018-08-15 昭和シェル石油株式会社 Ｃ重油組成物
US11788017B2 (en) 2017-02-12 2023-10-17 Magëmã Technology LLC Multi-stage process and device for reducing environmental contaminants in heavy marine fuel oil
US10604709B2 (en) 2017-02-12 2020-03-31 Magēmā Technology LLC Multi-stage device and process for production of a low sulfur heavy marine fuel oil from distressed heavy fuel oil materials
US12025435B2 (en) 2017-02-12 2024-07-02 Magēmã Technology LLC Multi-stage device and process for production of a low sulfur heavy marine fuel oil
US12559689B2 (en) 2017-02-12 2026-02-24 Magēmā Technology LLC Multi-stage process and device for treatment heavy marine fuel and resultant composition and the removal of detrimental solids
US12281266B2 (en) 2017-02-12 2025-04-22 Magẽmã Technology LLC Heavy marine fuel oil composition
US10655074B2 (en) 2017-02-12 2020-05-19 Mag{hacek over (e)}m{hacek over (a)} Technology LLC Multi-stage process and device for reducing environmental contaminates in heavy marine fuel oil
US12071592B2 (en) 2017-02-12 2024-08-27 Magēmā Technology LLC Multi-stage process and device utilizing structured catalyst beds and reactive distillation for the production of a low sulfur heavy marine fuel oil
JP7549967B2 (ja) 2020-03-12 2024-09-12 コスモ石油株式会社 流動接触分解プロセスにおける流動接触分解残油のリサイクル方法及び精製油の製造方法

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CN103562357A (zh) 2014-02-05
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JP2012246356A (ja) 2012-12-13
JP5639532B2 (ja) 2014-12-10
CN103562357B (zh) 2015-08-19

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