WO2012132370A1 - Dispositif de fabrication et procédé de fabrication d'une huile légère hydrocarbonée - Google Patents

Dispositif de fabrication et procédé de fabrication d'une huile légère hydrocarbonée Download PDF

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WO2012132370A1
WO2012132370A1 PCT/JP2012/002033 JP2012002033W WO2012132370A1 WO 2012132370 A1 WO2012132370 A1 WO 2012132370A1 JP 2012002033 W JP2012002033 W JP 2012002033W WO 2012132370 A1 WO2012132370 A1 WO 2012132370A1
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hydrocarbon oil
group
elements
light hydrocarbon
metal oxide
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PCT/JP2012/002033
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Japanese (ja)
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智史 古田
朋之 平尾
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Ｊｘ日鉱日石エネルギー株式会社
一般財団法人石油エネルギー技術センター
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Priority to JP2013507162A priority Critical patent/JP5943906B2/ja
Priority to CA2831565A priority patent/CA2831565A1/fr
Publication of WO2012132370A1 publication Critical patent/WO2012132370A1/fr

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    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/002—Mixed oxides other than spinels, e.g. perovskite
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
    • B01J21/06—Silicon, titanium, zirconium or hafnium; Oxides or hydroxides thereof
    • B01J21/063—Titanium; Oxides or hydroxides thereof
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/02—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the alkali- or alkaline earth metals or beryllium
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/10—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of rare earths
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/16—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/32—Manganese, technetium or rhenium
    • B01J23/34—Manganese
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/745—Iron
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/75—Cobalt
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/74—Iron group metals
    • B01J23/755—Nickel
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J23/00—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00
    • B01J23/70—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/83—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with rare earths or actinides
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/30—Catalysts, in general, characterised by their form or physical properties characterised by their physical properties
    • 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
    • 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
    • C10G49/00—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00
    • C10G49/02—Treatment of hydrocarbon oils, in the presence of hydrogen or hydrogen-generating compounds, not provided for in a single one of groups C10G45/02, C10G45/32, C10G45/44, C10G45/58 or C10G47/00 characterised by the catalyst used
    • 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
    • C10G69/04—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 catalytic cracking in the absence of hydrogen
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J2523/00—Constitutive chemical elements of heterogeneous catalysts
    • 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
    • C10G2300/80—Additives
    • C10G2300/805—Water

Definitions

  • the present invention relates to a light hydrocarbon oil production method and a light hydrocarbon oil production apparatus, and in particular, produces a light hydrocarbon oil having a low olefin content by cracking the hydrocarbon oil without supplying hydrogen from outside the system.
  • the present invention relates to a method and an apparatus used in the process.
  • the hydrocracking method is a method for lightening a heavy hydrocarbon oil by bringing a heavy hydrocarbon oil and a hydrogenation catalyst into contact with each other in a high-temperature, high-pressure hydrogen atmosphere (for example, patents).
  • Reference 1 The thermal decomposition method is a method for lightening a heavy hydrocarbon oil without using a catalyst by thermally decomposing hydrocarbon molecules under high temperature conditions (see, for example, Patent Document 2).
  • the fluid catalytic cracking method is a method of reducing the weight of heavy hydrocarbon oil by bringing a flowing catalyst and heavy hydrocarbon oil into contact with each other (see, for example, Patent Document 3).
  • the hydrocracking method uses a large amount of high-pressure hydrogen gas for the cracking reaction, which requires a large-scale hydrogen gas production facility, resulting in an increase in cost.
  • the pyrolysis method a large amount of coke is generated and the aromatic ring is hardly cleaved, so that the production efficiency of light hydrocarbon oil is poor and the heavy hydrocarbon oil cannot be decomposed sufficiently. was there.
  • the fluid catalytic cracking method has a problem that the operating cost of the apparatus is high.
  • the hydrocracking method it was necessary to desulfurize and denitrogenate the heavy hydrocarbon oil in advance in order to prevent deterioration (poisoning) of the hydrogenation catalyst. Furthermore, in the thermal cracking method and fluid catalytic cracking method, there is almost no desulfurization reaction or denitrogenation reaction of hydrocarbon oil, so it is necessary to desulfurize and denitrogenate the heavy hydrocarbon oil in advance as in the hydrocracking method. was there. That is, the hydrocracking method, the thermal cracking method, and the fluid catalytic cracking method have a problem that a pretreatment of heavy hydrocarbon oil is required.
  • the present inventors have developed a method that can lighten hydrocarbon oil efficiently at low cost without desulfurizing and denitrogenating hydrocarbon oil in advance and without using high-pressure hydrogen gas.
  • the present inventors use a predetermined composite metal oxide as a hydrocarbon oil cracking catalyst, thereby decomposing a hydrocarbon oil in the presence of water without supplying hydrogen from outside the reaction system. It was newly found that it can be converted.
  • the hydrocarbon oil when the hydrocarbon oil is lightened using the hydrocarbon oil decomposition catalyst in the presence of water, the hydrocarbon oil is not desulfurized and denitrogenated in advance, and high-pressure hydrogen gas is not used. It is possible to obtain light hydrocarbon oil efficiently at low cost.
  • the hydrocarbon oil when the hydrocarbon oil is lightened in the presence of water using the hydrocarbon oil cracking catalyst, the olefin content of the obtained light hydrocarbon oil is low. It became clear that it was relatively high. That is, the light hydrocarbon oil obtained by lightening the hydrocarbon oil using the hydrocarbon oil decomposition catalyst has room for improvement in terms of reducing the olefin content and improving the oxidation stability. .
  • the present invention provides a low-cost light hydrocarbon oil with a low olefin content from hydrocarbon oil without desulfurizing and denitrifying the hydrocarbon oil as a raw material in advance and without using high-pressure hydrogen gas. It is an object of the present invention to provide a method and an apparatus that can be efficiently manufactured.
  • the present invention aims to advantageously solve the above-mentioned problems, and the light hydrocarbon oil production method of the present invention comprises a light carbonization process for producing a light hydrocarbon oil by decomposing a hydrocarbon oil.
  • a method for producing hydrogen oil comprising contacting a hydrocarbon oil with a hydrocarbon oil cracking catalyst composed of a composite metal oxide in the presence of water to decompose the hydrocarbon oil, including light hydrocarbon oil
  • a decomposition step for obtaining a reaction mixture and a hydrogenation step for hydrogenating light hydrocarbon oil in the reaction mixture by contacting the reaction mixture obtained in the decomposition step with a hydrogenation catalyst comprising a metal oxide. It is characterized by including.
  • the hydrogenation catalyst preferably contains anatase-type titanium dioxide.
  • the hydrocarbon oil decomposition catalyst comprises (A) a composite metal oxide having a perovskite structure, and (B) a composite metal oxide having a pseudo brookite structure. And (C) one element X selected from group IVA elements, group IIIA elements, group VIA elements and group VIIA elements, group IVA elements in the fourth to sixth periods, and group VIII elements in the fourth period
  • the “element abundance” refers to a solution obtained by dissolving the catalyst by ICP emission spectroscopic analysis, and from the obtained measurement value, the molar amount of each element in the catalyst in terms of simple metal. It can be obtained by calculating the concentration.
  • the “element abundance ratio (molar ratio)” can be obtained by calculating the calculated molar concentration ratio of each element (hereinafter, the element abundance ratio calculation method is “melt / ICP-AES method ”).
  • the composite metal oxide having the perovskite structure is LaAlO 3 , NiTiO 3 , CoTiO 3 , KTiO 3 , BaTiO 3 , SrTiO 3 , and these composite metals. It is preferably selected from the group consisting of complex metal oxides in which part of the metal element of the oxide is substituted with another metal element.
  • the composite metal oxide having the pseudo-brookite structure is preferably Fe 2 TiO 5 .
  • the element X is zirconium
  • the element Y 1 is cerium
  • the element Y 2 is selected from the group consisting of tungsten, iron, and manganese. It is preferable that
  • the present invention aims to advantageously solve the above-mentioned problems, and the light hydrocarbon oil production apparatus of the present invention is a light carbonization that decomposes a hydrocarbon oil to produce a light hydrocarbon oil.
  • An apparatus for producing hydrogen oil comprising: a reactor; a raw material supply means for supplying hydrocarbon oil into the reactor; and a water supply means for supplying water into the reactor.
  • the hydrocarbon oil, the water, and a hydrocarbon oil decomposition catalyst composed of a composite metal oxide are brought into contact with each other to decompose the hydrocarbon oil to obtain a reaction mixture containing light hydrocarbon oil, and the reaction It has a hydrogenation part which hydrogenates the light hydrocarbon oil in a reaction mixture by making the mixture and the hydrogenation catalyst which consists of metal oxides contact.
  • the hydrogenation catalyst preferably contains anatase-type titanium dioxide.
  • the hydrocarbon oil cracking catalyst comprises (A) a composite metal oxide having a perovskite structure, and (B) a composite metal oxide having a pseudo-brookite structure. And (C) one element X selected from group IVA elements, group IIIA elements, group VIA elements and group VIIA elements, group IVA elements in the fourth to sixth periods, and group VIII elements in the fourth period
  • the sum of (the presence of the element X with respect to y 1 + y 2) (a ratio of x) (x / (y 1 + y 2)) is,
  • the “element abundance” refers to a solution obtained by dissolving the catalyst by ICP emission spectroscopic analysis, and from the obtained measurement value, the molar amount of each element in the catalyst in terms of simple metal. It can be obtained by calculating the concentration.
  • the “element abundance ratio (molar ratio)” can be obtained by calculating the calculated molar concentration ratio of each element (hereinafter, the element abundance ratio calculation method is “melt / ICP-AES method ”).
  • the composite metal oxide having the perovskite structure is LaAlO 3 , NiTiO 3 , CoTiO 3 , KTiO 3 , BaTiO 3 , SrTiO 3 , and these composite metals. It is preferably selected from the group consisting of complex metal oxides in which part of the metal element of the oxide is substituted with another metal element.
  • the composite metal oxide having a pseudo-brookite structure is preferably Fe 2 TiO 5 .
  • the element X is zirconium
  • the element Y 1 is cerium
  • the element Y 2 is selected from the group consisting of tungsten, iron, and manganese. It is preferable that
  • olefins are contained from hydrocarbon oil without desulfurization and denitrification of the hydrocarbon oil as a raw material in advance and without using high-pressure hydrogen gas. A small amount of light hydrocarbon oil can be produced efficiently at low cost.
  • 2 is an X-ray diffraction spectrum of NiTiO 3 having a perovskite structure.
  • 2 is an X-ray diffraction spectrum of CoTiO 3 having a perovskite structure.
  • 2 is an X-ray diffraction spectrum of Fe 2 TiO 5 having a pseudo-brookite structure.
  • 2 is an X-ray diffraction spectrum of anatase-type TiO 2 .
  • the manufacturing method and manufacturing apparatus of the light hydrocarbon oil of this invention are used when cracking hydrocarbon oil and manufacturing light hydrocarbon oil. And in the manufacturing method and manufacturing apparatus of the light hydrocarbon oil of this invention, light hydrocarbon oil with little olefin content can be manufactured, without supplying hydrogen from the outside of a reaction system.
  • the hydrocarbon oil used as a raw material when producing the light hydrocarbon oil using the light hydrocarbon oil production method and production apparatus of the present invention is not particularly limited, and is usually obtained during petroleum refining.
  • heavy hydrocarbon oils such as pressure distillation residue and vacuum distillation residue.
  • T50 vol% distillation temperature
  • examples thereof include hydrocarbon oils having a temperature of 550 ° C. or lower and hydrocarbon oils having a T50 of 250 ° C. or higher and 550 ° C. or lower.
  • the light hydrocarbon oil production apparatus includes a reactor that decomposes a hydrocarbon oil that is a raw material into a light hydrocarbon oil having a low olefin content, and a hydrocarbon oil that is a raw material into the reactor. It is characterized by comprising raw material supply means for supplying and water supply means for supplying water into the reactor.
  • the light hydrocarbon oil production apparatus of the present invention includes a cracking unit that decomposes hydrocarbon oil in the reactor to obtain a reaction mixture containing the light hydrocarbon oil, and a light hydrocarbon oil in the reaction mixture. And a hydrogenation part for hydrogenation.
  • the "reaction mixture” refers to a mixture obtained through a hydrocarbon oil decomposition reaction, and the reaction mixture includes not only reaction products such as light hydrocarbon oil but also unreacted materials such as water. .
  • the cracking section is a region where hydrocarbon oil supplied by the raw material supply means, water supplied by the water supply means, and a hydrocarbon oil decomposition catalyst are brought into contact with each other to decompose the hydrocarbon oil.
  • the hydrogenation section is an area where the reaction mixture obtained in the cracking section and the hydrogenation catalyst are brought into contact with each other to hydrogenate the light hydrocarbon oil in the reaction mixture, thereby reducing the olefin content of the light hydrocarbon oil. is there.
  • the reactor of the light hydrocarbon oil production apparatus of the present invention is filled with at least two types of catalysts, a hydrocarbon oil decomposition catalyst and a hydrogenation catalyst.
  • the vicinity of the hydrocarbon oil cracking catalyst in the reactor serves as a cracking section, and the vicinity of the hydrogenation catalyst serves as a hydrogenation section.
  • the hydrogenation section the light hydrocarbon oil in the reaction mixture obtained in the cracking section is hydrogenated. Therefore, in the reactor of the light hydrocarbon oil production apparatus of the present invention, a hydrocarbon comprising a hydrocarbon oil cracking catalyst is used.
  • An oil cracking catalyst layer is disposed upstream of the reactor (a side to which hydrocarbon oil and water are supplied) from the hydrogenation catalyst layer made of a hydrogenation catalyst, or a hydrocarbon oil cracking catalyst. And hydrogenation catalyst are mixed.
  • the hydrocarbon oil cracking catalyst is a compound that functions as a catalyst when cracking hydrocarbon oil without supplying hydrogen from outside the system in the presence of water, for example, two or more metal oxides.
  • a composite metal oxide which is an oxide formed by composite can be used. Specifically, without being particularly limited, (A) a composite metal oxide having a perovskite structure (apatite type structure), (B) a pseudo brookite type structure (pseudo plate titanium stone type structure, “pseudo brookite” (C) a composite metal oxide containing predetermined elements X, Y 1 and Y 2 , or a composite metal oxide thereof (A) The mixture of (C) can be used as a hydrocarbon oil cracking catalyst.
  • the crystal structure of the composite metal oxide used as a hydrocarbon oil cracking catalyst can be evaluated using, for example, X-ray diffraction analysis.
  • X-ray diffraction analysis for example, when the crystal structure of a hydrocarbon oil cracking catalyst made of NiTiO 3 having a perovskite structure is evaluated, an X-ray diffraction spectrum as shown in FIG. 2 is obtained.
  • a diffraction peak peculiar to NiTiO 3 having a perovskite structure appears.
  • the composite metal oxide having a perovskite structure includes a composite metal oxide represented by the general formula: ABO 3 and a part of at least one of the A site element and the B site element of the composite metal oxide ABO 3.
  • the composite metal oxide having a perovskite structure has the following general formula (1): A 1-x A ′ x B 1-y B ′ y O 3- ⁇ (1) [In the formula, A represents one element selected from the group consisting of Group IA element, Group IIA element, Group IIIA element and Group VIII element, and A ′ represents a group composed of Group VA element and Group IIIB element.
  • At least one element selected from B represents one element selected from the group consisting of Group IIIB elements and Group IVA elements
  • B ′ represents a group consisting of Group VA elements and Group IIIB elements
  • ⁇ indicates the amount of oxygen deficiency.
  • the oxide represented by these can be mentioned. Note that the oxygen deficiency is a number at which the oxide represented by the general formula (1) becomes electrically neutral.
  • the atomic ratio y of the element B ′ is preferably 0.4 or less (0 ⁇ y ⁇ 0.4), more preferably 0.35 or less (0 ⁇ y ⁇ 0.35), More preferably, it is 0.25 or less (0 ⁇ y ⁇ 0.25).
  • the B site element is preferably one element selected from the group consisting of IIIB group elements when the A site element is a IIIA group element. Further, the B site element is preferably one element selected from the group consisting of an IVA group element when the A site element is an IA group element, an IIA group element or a VIII group element.
  • the composite metal oxide having a perovskite structure includes LaAlO 3 , NiTiO 3 , CoTiO 3 , KTiO 3 , BaTiO 3 , SrTiO 3 , or a metal element of these composite metal oxides (A site).
  • Examples thereof include composite metal oxides in which a part of the element and the B site element is substituted with another metal element.
  • the composite metal oxide having a pseudo-brookite structure is not particularly limited, and Fe 2 TiO 5 can be exemplified.
  • a predetermined element X, a predetermined element Y 1, as a composite metal oxide containing predetermined element Y 2 is (A) one element X selected from group IVA elements; (B) one element Y 1 selected from the group consisting of Group IIIA elements, Group VIA elements and Group VIIA elements, and Group IVA elements in the 4th to 6th periods and Group VIII elements in the 4th period (provided that Is an element different from the element X), (C) One element Y 2 selected from the group consisting of Group IIIA elements, Group VIA elements and Group VIIA elements, and Group IVA elements in the 4th to 6th periods and Group VIII elements in the 4th period (provided that Element X and element Y 1 are different elements).
  • the ratio (molar ratio) of the abundance of each element X, Y 1 , Y 2 in the catalyst determined by melting / ICP-AES method is (D) a ratio of abundance x of the element X to the total (y 1 + y 2) between the abundance y 2 abundance y 1 and the element Y 2 elements Y 1 is 0.5 to 2.0 (0 .5 ⁇ x / (y 1 + y 2 ) ⁇ 2.0)
  • E a ratio of abundance y 2 elements Y 2 relative abundance y 1 element Y 1 is 0.02 to 0.25 (0.02 ⁇ y 2 / y 1 ⁇ 0.25), A ratio can be mentioned.
  • the element X, the element Y 1 , and the element Y 2 are not particularly limited, and examples thereof include Ti, Zr, Ce, W, Mn, and Fe.
  • the composite metal oxide in which these elements are element X, element Y 1 or element Y 2 is, for example, a composite containing Zr as element X, Ce as element Y 1 , W, Fe or Mn as element Y 2. Mention may be made of metal oxides.
  • the element X, the element Y 1, the composite metal oxide containing element Y 2, it is particularly preferable element X is zirconium (Zr).
  • Zr zirconium
  • the structure of the composite metal oxide can be maintained even when the catalyst is used under high temperature and high pressure conditions. That is, in the case of a composite metal oxide (hydrocarbon oil cracking catalyst) in which the element X is Zr, it is composed of hydrothermally synthesized zeolite, silica, or ⁇ -alumina used for hydrocracking of hydrocarbon oil. Like a hydrogenation catalyst, the crystal structure of the catalyst is not greatly changed by high-temperature and high-pressure steam, and the catalyst is not usable.
  • the catalyst is hardly deteriorated, and it is not necessary to pretreat the hydrocarbon oil (desulfurization and denitrogenation).
  • the molar ratio (x / m) of the abundance x of the element X to the abundance m of all the metal elements in the catalyst is 0.55 or more. It is preferable that it is 0.60 or more.
  • the above-described composite metal oxide can be prepared using a known method such as a coprecipitation method or a sol-gel method.
  • the composite metal oxide can be prepared as follows without any particular limitation.
  • the obtained precipitate is filtered and dried, and then the dried precipitate is fired to obtain a composite metal oxide.
  • the temperature for drying the precipitate in (iii) is preferably 100 ° C. or higher from the viewpoint of efficiently evaporating moisture, and 160 ° C. or lower from the viewpoint of preventing rapid drying. preferable.
  • the temperature at which the dried precipitate is calcined is the structural stability of the resulting composite metal oxide (catalyst) (ie, suppression of structural change of the composite metal oxide when hydrocarbon oil is decomposed using the catalyst). From the viewpoint of the above, it is preferably 500 ° C. or higher, and from the viewpoint of suppressing the reduction of the surface area of the composite metal oxide to be generated, it is preferably 900 ° C. or lower.
  • a compound that functions as a catalyst when hydrogenating the light hydrocarbon oil in the reaction mixture for example, a metal oxide
  • a metal oxide for example, anatase-type titanium dioxide (TiO 2 ) or a mixture containing anatase-type titanium dioxide can be used as a hydrogenation catalyst.
  • the anatase-type titanium dioxide used as a hydrogenation catalyst or a mixture containing anatase-type titanium dioxide is not particularly limited, and anatase-type titanium dioxide or anatase-type titanium dioxide is used.
  • the mixture containing nickel, cobalt, molybdenum or oxides supported thereon examples of the mixture containing nickel, cobalt, molybdenum or oxides supported thereon.
  • the total amount of titanium dioxide in the mixture is preferably 50% by mass or more, and more preferably 55% by mass or more of the mixture. It is preferably 60% by mass or more.
  • the light hydrocarbon oil production apparatus 1 shown in FIG. 1 includes a reactor 2, a raw material supply pump 3 as a raw material supply means, and a water supply pump 4 as a water supply means. Then, the reactor 2 of the light hydrocarbon oil production apparatus 1 is formed by filling the catalyst layer 21 for cracking hydrocarbon oil formed by filling the catalyst for cracking hydrocarbon oil and the catalyst for hydrogenation inside. And a hydrogenation catalyst layer 22.
  • one layer of hydrocarbon oil decomposition catalyst layer 21 is located upstream of one layer of hydrogenation catalyst layer 22 (the side to which heavy hydrocarbon oil and water are supplied).
  • a plurality of hydrocarbon oil decomposition catalyst layers and a plurality of hydrogenation catalyst layers are alternately and most upstreamly located. You may arrange
  • a mixed layer in which a hydrocarbon oil cracking catalyst and a hydrogenation catalyst are mixed may be disposed in the reactor.
  • the container filled with the hydrocarbon oil cracking catalyst and the container filled with the hydrogenation catalyst are arranged upstream of the container filled with the hydrogenation catalyst. It is good also as a reactor by connecting so that it may be located in the side.
  • the raw material supply pump 3 supplies the water supplied from the water supply pump 4.
  • the resulting heavy hydrocarbon oil and the hydrocarbon oil decomposition catalyst come into contact with each other, and the heavy hydrocarbon oil is decomposed (decomposition step).
  • disassembling the high molecular weight hydrocarbon compound in heavy hydrocarbon oil is obtained.
  • the reaction mixture containing the light hydrocarbon oil and the hydrogenation catalyst are contacted, and the light hydrocarbon oil in the reaction mixture is hydrogenated,
  • the olefin content of light hydrocarbon oil is reduced (hydrogenation process).
  • the reason why the heavy hydrocarbon oil can be decomposed in the presence of water in the decomposition step is not clear, but the composite metal oxide as described above, particularly a composite metal oxide having a perovskite structure, In addition, a composite metal oxide having a pseudo-brookite structure or a composite metal oxide containing the predetermined elements X, Y 1 and Y 2 has a high lattice oxygen supply rate, and decomposes water to release oxygen and hydrogen. This is presumed to be due to their high ability. That is, when these composite metal oxides decompose heavy hydrocarbon compounds using water as a hydrogen source, a part of the hydrocarbon compounds and water react as shown in the following reaction formula to generate hydrogen. This is presumed to be because the generation of hydrogen as a source can be promoted.
  • the heavy hydrocarbon oil is decomposed to become a light hydrocarbon oil, but this light hydrocarbon oil contains a relatively large amount of olefin and has low oxidation stability.
  • the reason why the light hydrocarbon oil contains a relatively large amount of olefin is not clear, but is presumably because the hydrogenation ability of the composite metal oxide used as the catalyst for cracking hydrocarbon oil is low. . That is, when the hydrocarbon oil cracking catalyst supplies lattice oxygen to decompose heavy hydrocarbon oil, hydrogenation using hydrogen generated by cracking water cannot be sufficiently advanced. Inferred.
  • the amount of water used when producing light hydrocarbon oil using the light hydrocarbon oil production apparatus may be an amount sufficient to lighten the hydrocarbon oil used as a raw material. It is desirable to add water at a ratio of 5 to 2000 parts by mass, preferably 10 to 1000 parts by mass, and more preferably 10 to 500 parts by mass with respect to 100 parts by mass of the oil. This is because when the amount of water added to 100 parts by mass of the hydrocarbon oil is less than 5 parts by mass, the hydrogen source may be insufficient and the hydrocarbon oil may not be sufficiently lightened.
  • the temperature in the reactor of the light hydrocarbon oil production apparatus can be set to a relatively low temperature, for example, 300 to 600 ° C., preferably 350 to 550 ° C., more preferably 400 to 500 ° C. This is because when the temperature is lower than 300 ° C., the activation energy necessary for the reaction cannot be obtained, and the decomposition of the hydrocarbon oil and the hydrogenation of the light hydrocarbon oil may not sufficiently proceed. Further, when the temperature is higher than 600 ° C., a large amount of unnecessary gas (methane, ethane, etc.) is generated, and the decomposition efficiency of hydrocarbon oil may be lowered.
  • a relatively low temperature for example, 300 to 600 ° C., preferably 350 to 550 ° C., more preferably 400 to 500 ° C.
  • the pressure in the reactor can be, for example, 0.1 to 40 MPa, preferably 0.1 to 35 MPa, and more preferably 0.1 to 30 MPa. This is because when the pressure is less than 0.1 MPa, it may be difficult to smoothly flow the hydrocarbon oil and water into the reactor. Moreover, it is because the manufacturing cost of a reactor may become high when a pressure exceeds 40 Mpa.
  • the liquid space velocity (LHSV) when circulating hydrocarbon oil and water in the reactor is, for example, 0.01 to 10 h ⁇ 1 , preferably 0.05 to 5 h ⁇ 1 , more preferably 0.1 to 2 h. ⁇ 1 .
  • the volume ratio (B / A) of the amount (B) of the hydrogenation catalyst to the amount (A) of the hydrocarbon oil cracking catalyst in the reactor can be 0.1 to 1.0. This is because if the amount of the hydrocarbon oil decomposition catalyst is small, the decomposition of the hydrocarbon oil may not sufficiently proceed. Further, if the amount of the hydrogenation catalyst is too large, the amount of the catalyst that does not contribute to the hydrogenation of the light hydrocarbon oil increases, and the production efficiency of the light hydrocarbon oil decreases.
  • hydrogen necessary for the hydrocarbon oil cracking reaction or light hydrocarbon oil hydrogenation reaction is present in the system.
  • the ratio (hydrogenation amount / hydrocarbon oil supply amount) can be 0.1 or less, preferably 0.
  • the light hydrocarbon oil production method and production apparatus of the present invention since the light hydrocarbon oil produced by cracking the hydrocarbon oil is hydrogenated, the light hydrocarbon having a low olefin content and excellent oxidation stability Oil can be obtained. Therefore, according to the light hydrocarbon oil production method and production apparatus of the present invention, light hydrocarbon oil having a low olefin content can be efficiently decomposed at low cost without using high-pressure hydrogen gas. Can be obtained.
  • the hydrocarbon oil decomposition catalyst used in the light hydrocarbon oil production method and production apparatus of the present invention is not easily deteriorated, the light hydrocarbon oil production method and production apparatus of the present invention using the catalyst is used. According to this, it is not necessary to desulfurize and denitrify the raw hydrocarbon oil to be decomposed in advance.
  • the manufacturing method of the light hydrocarbon oil of this invention and the manufacturing apparatus of light hydrocarbon oil are not limited to the said embodiment,
  • the light hydrocarbon oil of this invention The production method and the production apparatus for light hydrocarbon oil can be modified as appropriate.
  • the hydrogenation of the light hydrocarbon oil in the reaction mixture may be performed after removing water remaining in the reaction mixture after the decomposition of the hydrocarbon oil.
  • hydrocarbon oil decomposition catalyst did.
  • a hydrocarbon oil cracking catalyst was analyzed by an X-ray diffractometer, a diffraction peak peculiar to Fe 2 TiO 5 having a pseudo-brookite structure as shown in FIG. 4 (indicated by an arrow in the figure) X-ray diffraction spectrum having) was obtained. That is, it was found that the prepared hydrocarbon oil cracking catalyst was composed of Fe 2 TiO 5 having a pseudo-brookite structure.
  • a hydrogenation catalyst (catalyst a) comprising anatase-type titanium dioxide was prepared.
  • titanium sulfate was dissolved in ion-exchanged water, and ammonia water was added dropwise to form a precipitate.
  • the resulting precipitate was aged (still kept overnight at 40 ° C.), filtered and dried (6 hours in an air atmosphere at 130 ° C.), and then the dried precipitate was calcined at a temperature of 600 ° C. for hydrogenation.
  • a catalyst was prepared. When the obtained hydrogenation catalyst was analyzed with an X-ray diffractometer, a diffraction peak (indicated by an arrow in the figure) corresponding to the (101) plane of anatase TiO 2 as shown in FIG. 5 was obtained.
  • the prepared hydrogenation catalyst was composed of anatase-type titanium dioxide.
  • the upper layer (upstream side) of the superalloy (Inconel 625) reactor (internal volume 10 mL) was filled with 8.0 mL of hydrocarbon decomposition catalyst, and the lower layer was charged with 2.0 mL of hydrogenation catalyst. .
  • the inside of the reactor was heated and pressurized to a temperature of 470 ° C. and a pressure of 15 MPa while passing ion exchange water through the reactor filled with the catalyst at a flow rate of 0.1 mL / min.
  • Example 3 A hydrocarbon oil decomposition catalyst (catalyst C) made of a composite metal oxide in which the element X is zirconium, the element Y 1 is cerium, and the element Y 2 is tungsten was prepared.
  • ammonium metatungstate was dissolved in ion-exchanged water to obtain an aqueous solution of ammonium metatungstate having a predetermined concentration.
  • an aqueous ammonium metatungstate solution was added dropwise to the aqueous solution containing Zr, Ce while adjusting the aqueous solution so that the pH of the aqueous solution did not exceed 8, thereby generating a precipitate.
  • Example 2 A hydrocarbon oil cracking catalyst comprising the composite metal oxide contained was prepared.
  • Zr: Ce: W 49: 48: 3.
  • a hydrogenation catalyst (catalyst a) comprising anatase-type titanium dioxide was prepared.
  • Example 2 In the same manner as in Example 1, a hydrogenation catalyst (catalyst a) comprising anatase-type titanium dioxide was prepared. And the heavy hydrocarbon oil was decomposed
  • Table 2 shows that the light hydrocarbon oils produced in Examples 1 to 4 have a lower olefin content than the light hydrocarbon oils produced in Comparative Examples 1 to 4.
  • Example 5 The light hydrocarbon obtained by decomposing the heavy hydrocarbon oil in the same manner as in Example 3 except that the temperature and pressure in the reactor when decomposing the heavy hydrocarbon oil were changed as shown in Table 3. The properties of hydrogen oil were evaluated in the same manner as in Example 1. The results are shown in Table 3 in comparison with Comparative Example 3.
  • Example 5 has less olefin content than the light hydrocarbon oil produced in Comparative Example 3.
  • Example 5 In order to evaluate the deterioration resistance of the catalyst, in Example 5, the decomposition of the heavy hydrocarbon oil was continued for 14 days or more. Then, after 14 days from the start of oil passing, the effluent from the reactor was collected for 1 hour, and the olefin content (index of olefin attributed carbon content) was calculated in the same manner as in Example 1. Table 4 shows the index of the olefin attributed carbon amount after 6 hours from the start of oil passing and the index of the olefin attributed carbon amount after 14 days from the start of oil passing.
  • Example 5 shows that in Example 5, the amount of olefin attributed carbon after 6 hours from the start of oil passing and the amount of olefin attributed carbon after 14 days from the start of oil passing changed significantly. Therefore, in Example 5, it turns out that deterioration of a catalyst is suppressed.
  • olefins are contained from hydrocarbon oil without desulfurization and denitrification of the hydrocarbon oil as a raw material in advance and without using high-pressure hydrogen gas. A small amount of light hydrocarbon oil can be produced efficiently at low cost.

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

Abstract

La présente invention a pour but de proposer un dispositif et un procédé qui sont aptes à produire efficacement à un faible coût à partir d'une huile hydrocarbonée une huile légère hydrocarbonée ayant une faible quantité d'oléfines contenues. Le procédé de fabrication d'une huile légère hydrocarbonée comprend : une étape de craquage pour craquer l'huile hydrocarbonée en amenant en contact l'huile hydrocarbonée et un catalyseur de craquage d'huile hydrocarbonée en présence d'eau ; et une étape d'hydrogénation pour amener en contact le mélange réactionnel obtenu dans l'étape de craquage et un catalyseur d'hydrogénation afin d'hydrogéner l'huile légère hydrocarbonée dans le mélange réactionnel. Egalement, le dispositif de fabrication d'une huile légère hydrocarbonée comporte : un récipient de réaction ; un moyen d'alimentation en matière de départ qui fournit l'huile hydrocarbonée au récipient de réaction ; et un moyen d'alimentation en eau qui fournit de l'eau au récipient de réaction. Le récipient de réaction comporte : une section de craquage pour obtenir un produit de réaction contenant une huile légère hydrocarbonée par craquage de l'huile hydrocarbonée en amenant en contact l'huile hydrocarbonée, l'eau et le catalyseur de craquage d'huile hydrocarbonée ; et une section d'hydrogénation pour hydrogéner l'huile légère hydrocarbonée dans le mélange de réaction en amenant en contact le mélange de réaction et le catalyseur d'hydrogénation.
PCT/JP2012/002033 2011-03-31 2012-03-23 Dispositif de fabrication et procédé de fabrication d'une huile légère hydrocarbonée WO2012132370A1 (fr)

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