WO2012132318A1 - Catalyseur pour une décomposition d'huile hydrocarbonée et procédé de décomposition d'une huile hydrocarbonée - Google Patents

Catalyseur pour une décomposition d'huile hydrocarbonée et procédé de décomposition d'une huile hydrocarbonée Download PDF

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WO2012132318A1
WO2012132318A1 PCT/JP2012/001920 JP2012001920W WO2012132318A1 WO 2012132318 A1 WO2012132318 A1 WO 2012132318A1 JP 2012001920 W JP2012001920 W JP 2012001920W WO 2012132318 A1 WO2012132318 A1 WO 2012132318A1
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hydrocarbon oil
group
catalyst
oxide
decomposition
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PCT/JP2012/001920
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English (en)
Japanese (ja)
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朋之 平尾
智史 古田
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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 CA2831537A priority Critical patent/CA2831537A1/fr
Publication of WO2012132318A1 publication Critical patent/WO2012132318A1/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
    • B01J23/70—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
    • B01J23/002—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
    • 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
    • B01J23/76—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36
    • B01J23/84—Catalysts comprising metals or metal oxides or hydroxides, not provided for in group B01J21/00 of the iron group metals or copper combined with metals, oxides or hydroxides provided for in groups B01J23/02 - B01J23/36 with arsenic, antimony, bismuth, vanadium, niobium, tantalum, polonium, chromium, molybdenum, tungsten, manganese, technetium or rhenium
    • B01J23/847—Vanadium, niobium or tantalum or polonium
    • B01J23/8472—Vanadium
    • 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
    • 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 hydrocarbon oil cracking catalyst and a hydrocarbon oil cracking method, and in particular, a catalyst used for cracking and lightening a hydrocarbon oil without supplying hydrogen from outside the system, and the catalyst.
  • the present invention relates to a method for cracking hydrocarbon oil.
  • 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 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 invention provides a hydrocarbon oil cracking that can efficiently lighten a hydrocarbon oil at low cost without desulfurizing and denitrifying the hydrocarbon oil in advance and without using high-pressure hydrogen gas. It is an object to provide a catalyst for hydrocarbons and a method for cracking hydrocarbon oil.
  • the present inventors have intensively studied to solve the above problems, and by using a catalyst made of an oxide having a specific crystal structure, hydrocarbon oil can be used in the presence of water without using hydrogen gas.
  • the present invention has been completed.
  • the present invention aims to advantageously solve the above-mentioned problems, and the hydrocarbon oil cracking catalyst of the present invention is used when cracking hydrocarbon oil in the presence of water, and is a perovskite. It is characterized by comprising an oxide having a mold structure, an oxide having a pseudo-brookite structure, or a mixture thereof.
  • the perovskite-type oxide has a general formula: A 1-x A ′ x B 1-y B ′ y O 3- ⁇ [where A is , A group selected from the group consisting of group IA elements, group IIA elements, group IIIA elements and group VIII elements, and A ′ is at least one selected from the group consisting of group VA elements and group IIIB elements B represents one element selected from the group consisting of Group IIIB elements and Group IVA elements, and B ′ represents at least one selected from the group consisting of Group VA elements and Group IIIB elements.
  • A, A ′, B, and B ′ are elements different from each other, x is a numerical value range of 0 ⁇ x ⁇ 0.4, and y is a numerical value of 0 ⁇ y ⁇ 0.4.
  • ⁇ represents the amount of oxygen deficiency. It is preferable that it is an oxide represented by this.
  • the A is nickel or cobalt
  • the B is titanium
  • the B ′ is aluminum or vanadium.
  • x 0.
  • the pseudo-brookite structure oxide is preferably Fe 2 TiO 5 .
  • the present invention aims to advantageously solve the above-described problems, and the hydrocarbon oil cracking method of the present invention comprises a hydrocarbon oil and the above-mentioned hydrocarbon oil cracking in the presence of water. Hydrocarbon oil is decomposed by contacting with any of the catalysts.
  • the hydrocarbon oil as a raw material is not desulfurized and denitrogenated in advance, and high-pressure hydrogen gas is not used at low cost.
  • the hydrocarbon oil can be lightened efficiently.
  • 2 is an X-ray diffraction spectrum of NiTi 0.75 Al 0.25 O 2.875 having a perovskite structure.
  • 2 is an X-ray diffraction spectrum of NiTiO 3 having a perovskite structure.
  • 2 is an X-ray diffraction spectrum of CoTi 0.75 V 0.25 O 3.125 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 a mixture of NiO and rutile TiO 2 .
  • 2 is an X-ray diffraction spectrum of a mixture of Fe 2 O 3 , rutile TiO 2 and anatase TiO 2 .
  • the hydrocarbon oil cracking catalyst of the present invention is used when cracking and lightening hydrocarbon oil.
  • the hydrocarbon oil is brought into contact with the hydrocarbon oil cracking catalyst in the presence of water without supplying hydrogen from outside the reaction system. Decomposes to produce light hydrocarbon oil.
  • the hydrocarbon oil to be decomposed (lightened) using the hydrocarbon oil cracking catalyst of the present invention is not particularly limited, and is an atmospheric distillation residue or a vacuum distillation residue obtained during petroleum refining.
  • hydrocarbon oil having a 50 vol% distillation temperature (T50) in atmospheric distillation of 150 ° C. or higher and 550 ° C. or lower, or T50 can be mentioned hydrocarbon oils having a temperature of 200 ° C. or more and 550 ° C. or less, and hydrocarbon oils having a T50 of 250 ° C. or more and 550 ° C. or less.
  • the hydrocarbon oil cracking catalyst of the present invention is referred to as an oxide of a perovskite type structure (apatite type structure) or a pseudo brookite type structure (pseudo plate titanium stone type structure, “pseudo brookite type structure”). Or a mixture of an oxide having a perovskite structure and an oxide having a pseudo-brookite structure.
  • the crystal structure of the oxide can be evaluated using, for example, X-ray diffraction analysis. Specifically, whether or not the oxide has a perovskite structure can be determined by whether or not a peak peculiar to the perovskite structure appears in the X-ray diffraction spectrum. Whether or not the oxide has a pseudo-brookite structure can be determined by whether or not a peak peculiar to the pseudo-brookite structure appears in the X-ray diffraction spectrum.
  • an oxide having a perovskite structure or an oxide having a pseudo-brookite structure is used as a hydrocarbon oil decomposition catalyst. If these oxides are used as a catalyst, water is used as a hydrogen source for carbonization. This is based on the novel knowledge of the present inventors that hydrogen compounds can be decomposed efficiently. The reason why hydrocarbon compounds can be efficiently decomposed by using these oxides as a catalyst is not clear, but oxides having a perovskite structure or oxides having a pseudo-brookite structure are lattice oxygen This is presumed to be because of the high supply rate and the ability to decompose water and release oxygen and hydrogen.
  • a composite oxide represented by the general formula: ABO 3 or a part of at least one of the A site element and the B site element of the composite oxide ABO 3 may be another element.
  • a composite oxide obtained by substituting with Specifically, as an oxide having a perovskite structure, 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 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
  • At least one element selected from A, A ′, B, and B ′ are different from each other
  • x is a numerical range of 0 ⁇ x ⁇ 0.4
  • y is 0 ⁇ y ⁇ 0.4 is a numerical range
  • ⁇ 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 oxide having a perovskite structure may be a composite oxide in which a part of the A-site element or B-site element is substituted with other elements A ′ and B ′.
  • a complex oxide in which the site element and the B site element are not substituted may be used.
  • the atomic ratio y of the element B ′ is preferably 0.4 or less (y ⁇ 0.4), more preferably 0.35 or less (y ⁇ 0.35), and 0.25 or less. It is particularly preferable that (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 element A can be, for example, nickel, cobalt, barium, or the like.
  • the element B can be, for example, zirconium, cerium, titanium, or the like.
  • the element B ′ can be, for example, aluminum or vanadium.
  • the element A is preferably nickel or cobalt, for example.
  • the element B is preferably, for example, zirconium, cerium or titanium.
  • the element B ′ is preferably aluminum or vanadium, for example. Since the hydrocarbon oil cracking catalyst of the present invention is used in the presence of water, the element constituting the oxide is preferably an element that has a low ionization tendency and is stable in water, for example, a transition metal element. is there.
  • the oxide (composite oxide) having the perovskite structure as described above is not particularly limited and can be prepared, for example, by the coprecipitation method as follows.
  • a compound containing element A, a compound containing element B, and, if necessary, a compound containing element A ′ and a compound containing element B ′ for example, A ′ / A is 0 to 2 / 3 (molar ratio) and dissolved in ion-exchanged water in such an amount that B ′ / B is 0 to 2/3 (molar ratio).
  • Element A, element B, and optionally element A ′ And an aqueous solution containing the element B ′.
  • a coprecipitation agent such as aqueous ammonia or sodium carbonate solution is added to the prepared aqueous solution so that the pH of the aqueous solution does not deviate toward the alkali side (for example, the pH is in the range of 5 to 8).
  • a coprecipitation agent such as aqueous ammonia or sodium carbonate solution is added to the prepared aqueous solution so that the pH of the aqueous solution does not deviate toward the alkali side (for example, the pH is in the range of 5 to 8).
  • the obtained precipitate is filtered and dried, and then the dried precipitate is fired to obtain a composite oxide having a perovskite structure.
  • the temperature at which the precipitate is dried in the above (iii) is preferably 100 ° C. or higher from the viewpoint of efficiently evaporating moisture.
  • the temperature for drying the precipitate is preferably 160 ° C. or less from the viewpoint of preventing rapid drying.
  • the temperature at which the dried precipitate is calcined is determined from the viewpoint of the structural stability of the resulting composite oxide (catalyst) (that is, suppression of structural change of the composite oxide when hydrocarbon oil is decomposed by using it as a catalyst). Is preferably 500 ° C. or higher.
  • the temperature which bakes a precipitate is 900 degrees C or less from a viewpoint of suppressing the reduction
  • the oxide having a pseudo-brookite structure that is the hydrocarbon oil cracking catalyst of the present invention is not particularly limited, and examples thereof include a composite oxide Fe 2 TiO 5 .
  • Fe 2 TiO 5 having a pseudo-brookite structure is not particularly limited, and can be prepared by a coprecipitation method, for example, as follows.
  • a coprecipitation agent such as aqueous ammonia or sodium carbonate solution is added to the prepared aqueous solution so that the pH of the aqueous solution does not deviate to the alkali side (for example, the pH is in the range of 5 to 8).
  • the temperature for drying the precipitate is preferably 100 ° C. or higher from the viewpoint of efficiently evaporating moisture. Further, the temperature for drying the precipitate is preferably 160 ° C. or less from the viewpoint of preventing rapid drying.
  • the temperature at which the dried precipitate is calcined is determined from the viewpoint of the structural stability of the resulting composite oxide (catalyst) (that is, suppression of structural change of the composite oxide when hydrocarbon oil is decomposed by using it as a catalyst). Is preferably 500 ° C. or higher. Furthermore, it is preferable that the temperature which bakes a precipitate is 900 degrees C or less from a viewpoint of suppressing the reduction
  • the above-mentioned oxide having a perovskite structure or an oxide having a pseudo-brookite structure can be prepared by using a known method such as a sol-gel method in addition to the coprecipitation method.
  • the hydrocarbon oil is cracked by bringing the hydrocarbon oil into contact with the above-described hydrocarbon oil cracking catalyst in the presence of water.
  • a mixture of a hydrocarbon oil and water is circulated in a reactor filled with the catalyst, whereby a catalyst, a hydrocarbon oil, To contact hydrocarbons and decompose hydrocarbon oil.
  • the water used for the decomposition of the hydrocarbon oil is to decompose the high molecular weight hydrocarbon compound contained in the hydrocarbon oil into a lower molecular weight hydrocarbon compound, that is, to lighten the hydrocarbon oil.
  • the amount of water used may be an amount sufficient to lighten the hydrocarbon oil.
  • the conditions for bringing the mixture of the hydrocarbon oil and water into contact with the catalyst in the reactor can be appropriately changed.
  • the temperature at which the mixture and the catalyst are brought into contact with each other can be relatively low, 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., activation energy necessary for the reaction cannot be obtained, and decomposition of the 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 the hydrocarbon oil may be lowered.
  • the pressure at the time of bringing the mixture into contact with the catalyst 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. Furthermore, the liquid hourly space velocity (LHSV) when the mixture is circulated through the reactor filled with the catalyst is, for example, 0.01 to 10 h ⁇ 1 , preferably 0.05 to 5 h ⁇ 1 , more preferably 0.1 to 2 h. ⁇ 1 .
  • LHSV liquid hourly space velocity
  • hydrogen necessary for the hydrocarbon oil cracking reaction can be supplied from water existing in the system. Accordingly, in the hydrocarbon oil cracking method of the present invention, it is not necessary to add hydrogen from outside the system, but the molar ratio between the amount of hydrogen added from outside the system and the amount of hydrocarbon oil to be cracked (hydrogen addition) Amount / hydrocarbon oil supply amount) can be 0.1 or less, preferably 0. Therefore, according to the hydrocarbon oil cracking method of the present invention using the hydrocarbon oil cracking catalyst of the present invention, without using high-pressure hydrogen gas, the hydrocarbon oil is efficiently cracked at low cost, Light hydrocarbons can be obtained.
  • hydrocarbon oil cracking method of the present invention for example, condensed polycyclic aromatic compounds such as 1-methylnaphthalene, quinoline, anthracene and phenanthrene, and non-condensed polycyclic compounds such as dibenzothiophene and biphenyl.
  • a heavy hydrocarbon oil comprising a mixture of various hydrocarbon compounds such as aromatic compounds is decomposed to obtain a light hydrocarbon oil having a weight average molecular weight of not more than half that of the heavy hydrocarbon oil, preferably not more than 1/3. be able to.
  • a light hydrocarbon oil can be produced by cleaving an aromatic ring of a hydrocarbon compound in a heavy hydrocarbon oil with a very high probability to obtain a monocyclic aromatic compound.
  • a weight average molecular weight means the polystyrene conversion value measured using gel permeation chromatography (GPC).
  • the hydrocarbon oil cracking catalyst of the present invention since the hydrocarbon oil cracking catalyst of the present invention is hardly deteriorated, the hydrocarbon oil cracking method of the present invention using the catalyst needs to desulfurize and denitrogenate the raw hydrocarbon oil to be cracked in advance. There is no.
  • disassembly method of hydrocarbon oil are not limited to the said embodiment,
  • disassembly of this invention and A change can be suitably added to the decomposition method of hydrocarbon oil.
  • the obtained precipitate is aged (still for 1 hour), filtered and dried (150 ° C., 1 hour), and then the dried precipitate is calcined at a temperature of 800 ° C. to prepare a catalyst comprising a composite oxide.
  • a catalyst comprising a composite oxide.
  • the obtained composite oxide was analyzed with an X-ray diffractometer, a diffraction peak peculiar to NiTi 0.75 Al 0.25 O 2.875 having a perovskite structure as shown in FIG.
  • An X-ray diffraction spectrum having (indicated by an arrow) was obtained. That is, it was found that the prepared catalyst was NiTi 0.75 Al 0.25 O 2.875 having a perovskite type structure.
  • the prepared catalyst was packed in a stainless steel reactor (internal volume 10 mL) at a bulk density of 0.908 g / cm 3 .
  • the inside of the reactor was heated and pressurized to a temperature of 470 ° C. and a pressure of 0.10 MPaG while passing ion exchange water through the reactor filled with the catalyst at a flow rate of 0.1 mL / min.
  • the decomposition rate Cv of the fraction having a boiling point of 380 ° C. or higher in the supplied heavy hydrocarbon oil was calculated using the following formula. Coke was measured by a combustion ultraviolet fluorescence method.
  • Cv Decomposition ratio [mass%] of a fraction having a boiling point of 380 ° C. or higher in heavy hydrocarbon oil
  • F Amount of the fraction having a boiling point of 380 ° C. or higher in the supplied heavy hydrocarbon [g / h]
  • R The amount of the fraction having a boiling point of 380 ° C. or higher in the decomposition reaction product [g / h]
  • Coke amount of carbonaceous matter deposited on the catalyst [g / h]
  • Example 2 A catalyst was prepared in the same manner as in Example 1 except that the B site was not substituted, that is, aluminum nitrate was not added. And the heavy hydrocarbon oil was decomposed
  • the obtained catalyst was analyzed in the same manner as in Example 1. As a result, X-ray diffraction having a diffraction peak (indicated by an arrow in the figure) peculiar to NiTiO 3 having a perovskite structure as shown in FIG. A spectrum was obtained. That is, it was found that the prepared catalyst was NiTiO 3 having a perovskite type structure.
  • the obtained composite oxide was analyzed with an X-ray diffractometer, it has a diffraction peak (indicated by an arrow in the figure) characteristic of Fe 2 TiO 5 having a pseudo-brookite structure as shown in FIG.
  • An X-ray diffraction spectrum was obtained. That is, it was found that the prepared catalyst was Fe 2 TiO 5 having a pseudo-brookite structure.
  • the prepared catalyst was packed in a stainless steel reactor (internal volume 10 mL) at a bulk density of 0.904 g / cm 3 . Next, the inside of the reactor was heated and pressurized to a temperature of 470 ° C.
  • FIG. The results are shown in Table 2.
  • the obtained catalyst was analyzed with an X-ray diffractometer. As shown in FIG. 5, a diffraction peak peculiar to NiO (indicated by a solid arrow in the figure) and a diffraction peak peculiar to rutile TiO 2 were obtained.
  • a diffraction peak peculiar to Fe 2 O 3 (hematite) (shown by a solid line arrow in the figure) and a rutile type TiO (in the figure, indicated by a dotted arrow) diffraction peak peculiar to 2, (shown by dotted arrows) diffraction peak specific to the TiO 2 in anatase X-ray diffraction spectrum having a was obtained. That is, the catalyst was found to be a mixture of Fe 2 O 3 (hematite), rutile TiO 2 and anatase TiO 2 .
  • Table 2 shows that the catalysts of Examples 1 to 3 have a higher decomposition rate than the catalyst of Comparative Example 1. It can also be seen that the catalyst of Example 4 has a higher decomposition rate than the catalyst of Comparative Example 2.
  • Example 4 In order to evaluate the deterioration resistance of the catalyst, in Example 4 and Comparative Example 2, 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 2 hours, and the decomposition rate of the heavy hydrocarbon oil was calculated in the same manner as in Example 1. Table 3 shows the decomposition rate of heavy hydrocarbon oil 6 hours after the start of oil passing and the decomposition rate of heavy hydrocarbon oil 14 days after the start of oil passing.
  • Example 4 From Table 3, the decomposition rate after 6 hours from the start of oil passage and the decomposition rate after 14 days from the start of oil passage did not change much in Example 4, whereas in Comparative Example 2, the start of oil passage 14 It can be seen that the degradation rate after the passage of days has greatly decreased. Therefore, in Example 4, it turns out that deterioration of a catalyst is suppressed.
  • carbonization that can lighten hydrocarbon oil efficiently at low cost without previously desulfurizing and denitrifying hydrocarbon oil as a raw material and without using high-pressure hydrogen gas.
  • a catalyst for hydrogen oil decomposition can be provided.
  • the hydrocarbon oil cracking method using the hydrocarbon oil cracking catalyst can be provided.

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Abstract

La présente invention a pour but de pourvoir à un catalyseur pour une décomposition d'une huile hydrocarbonée apte à alléger efficacement une huile hydrocarbonée à faible coût et un procédé de décomposition d'une huile hydrocarbonée. Le catalyseur de décomposition d'une huile hydrocarbonée de la présente invention est utilisé en décomposition de l'huile hydrocarbonée en présence d'eau, et caractérisé en ce qu'il comprend un oxyde ayant une structure de pérovskite ou un oxyde ayant une structure de pseudobrookite, ou un mélange de ceux-ci. Le procédé de décomposition d'une huile hydrocarbonée de la présente invention est caractérisé par la mise en contact d'une huile hydrocarbonée avec le catalyseur de décomposition d'une huile hydrocarbonée en présence d'eau pour décomposer l'huile hydrocarbonée.
PCT/JP2012/001920 2011-03-31 2012-03-21 Catalyseur pour une décomposition d'huile hydrocarbonée et procédé de décomposition d'une huile hydrocarbonée WO2012132318A1 (fr)

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JP2011-080439 2011-03-31
JP2011080439A JP5687941B2 (ja) 2011-03-31 2011-03-31 炭化水素油分解用触媒および炭化水素油の分解方法

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JP5434998B2 (ja) * 2011-09-15 2014-03-05 トヨタ自動車株式会社 負極活物質、負極及び電池

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JPH08269464A (ja) * 1995-04-03 1996-10-15 Japan Energy Corp 炭化水素油の接触分解方法
JP2000140635A (ja) * 1998-09-03 2000-05-23 Gaz De France ペロブスカイト結晶構造を有する熱安定性の金属酸化物触媒およびその製造方法
JP2006007151A (ja) * 2004-06-29 2006-01-12 Ngk Insulators Ltd 重質油を軽質化するための触媒とその製造方法
JP2008297452A (ja) * 2007-05-31 2008-12-11 Japan Energy Corp アルキルベンゼン類の製造方法
JP2009102471A (ja) * 2007-10-22 2009-05-14 Japan Energy Corp 重質油の熱分解方法
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JPH08269464A (ja) * 1995-04-03 1996-10-15 Japan Energy Corp 炭化水素油の接触分解方法
JP2000140635A (ja) * 1998-09-03 2000-05-23 Gaz De France ペロブスカイト結晶構造を有する熱安定性の金属酸化物触媒およびその製造方法
JP2006007151A (ja) * 2004-06-29 2006-01-12 Ngk Insulators Ltd 重質油を軽質化するための触媒とその製造方法
JP2008297452A (ja) * 2007-05-31 2008-12-11 Japan Energy Corp アルキルベンゼン類の製造方法
JP2009102471A (ja) * 2007-10-22 2009-05-14 Japan Energy Corp 重質油の熱分解方法
JP2009242467A (ja) * 2008-03-28 2009-10-22 Japan Energy Corp 炭化水素油の分解方法

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