WO2010035710A1 - Agent desulfurant, son procede de production, et procede de desulfuration de l'huile d'hydrocarbure - Google Patents

Agent desulfurant, son procede de production, et procede de desulfuration de l'huile d'hydrocarbure Download PDF

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Publication number
WO2010035710A1
WO2010035710A1 PCT/JP2009/066374 JP2009066374W WO2010035710A1 WO 2010035710 A1 WO2010035710 A1 WO 2010035710A1 JP 2009066374 W JP2009066374 W JP 2009066374W WO 2010035710 A1 WO2010035710 A1 WO 2010035710A1
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Prior art keywords
nickel
zinc
desulfurization
desulfurizing agent
mass
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PCT/JP2009/066374
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English (en)
Japanese (ja)
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泰博 荒木
幸雄 大塚
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財団法人石油産業活性化センター
株式会社ジャパンエナジー
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Priority to JP2010530834A priority Critical patent/JP5284361B2/ja
Publication of WO2010035710A1 publication Critical patent/WO2010035710A1/fr

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    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G9/00—Compounds of zinc
    • C01G9/02—Oxides; Hydroxides
    • 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
    • B01J23/80—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 zinc, cadmium or mercury
    • 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
    • B01J35/391—Physical properties of the active metal ingredient
    • B01J35/393—Metal or metal oxide crystallite size
    • 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/612—Surface area less than 10 m2/g
    • 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/613—10-100 m2/g
    • 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/61—Surface area
    • B01J35/615—100-500 m2/g
    • 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/633—Pore volume less than 0.5 ml/g
    • 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
    • B01J35/60—Catalysts, in general, characterised by their form or physical properties characterised by their surface properties or porosity
    • B01J35/63—Pore volume
    • B01J35/635—0.5-1.0 ml/g
    • B—PERFORMING OPERATIONS; TRANSPORTING
    • B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
    • B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
    • B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
    • B01J37/02—Impregnation, coating or precipitation
    • B01J37/03—Precipitation; Co-precipitation
    • B01J37/031—Precipitation
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01G—COMPOUNDS CONTAINING METALS NOT COVERED BY SUBCLASSES C01D OR C01F
    • C01G53/00—Compounds of nickel
    • C01G53/04—Oxides; Hydroxides
    • 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
    • C10G25/00—Refining of hydrocarbon oils in the absence of hydrogen, with solid sorbents
    • C10G25/003—Specific sorbent material, not covered by C10G25/02 or C10G25/03
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2002/00—Crystal-structural characteristics
    • C01P2002/60—Compounds characterised by their crystallite size
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/12—Surface area
    • C—CHEMISTRY; METALLURGY
    • C01—INORGANIC CHEMISTRY
    • C01P—INDEXING SCHEME RELATING TO STRUCTURAL AND PHYSICAL ASPECTS OF SOLID INORGANIC COMPOUNDS
    • C01P2006/00—Physical properties of inorganic compounds
    • C01P2006/14—Pore volume

Definitions

  • the present invention relates to a desulfurizing agent used when desulfurizing sulfur compounds in hydrocarbon oil, a method for producing the desulfurizing agent, and a desulfurizing method for hydrocarbon oil using the desulfurizing agent.
  • the sulfur content of the fuel Reduction is increasingly required.
  • the sulfur content of gasoline and light oil is regulated to sulfur-free (sulfur content of 10 ppm by mass or less), and further low sulfur content, that is, zero sulfur (sulfur content of 1 ppm by mass or less) fuel oil is also sought. It has been.
  • hydrodesulfurization which is a desulfurization technique that has been used mainly in the past (for example, desulfurization in a high-temperature, high-pressure hydrogen atmosphere using an alumina catalyst supporting cobalt, nickel, and molybdenum), gasoline and diesel oil
  • hydrodesulfurization reaction which is a high temperature / high pressure reaction, has a higher Since operation at high pressure is required, energy consumption increases and hydrogen consumption also becomes enormous. Further, in the above hydrodesulfurization, if an attempt is made to react under mild conditions by reducing the space velocity, a huge amount of catalyst is required.
  • nickel is supported on a mixture of zinc oxide, alumina and nacre as a desulfurization agent for desulfurizing catalytic cracking gasoline (gasoline fraction obtained from fluid catalytic cracking unit) while suppressing octane loss.
  • a desulfurizing agent has been proposed (Patent Document 1). However, since this desulfurizing agent has a small specific surface area, a sufficient desulfurization level cannot be obtained, and a high reaction temperature of 300 ° C. or higher is required.
  • catalytic cracking gasoline can be highly desulfurized by desulfurization under specific conditions using a desulfurization agent containing nickel and zinc (Patent Document 3, 4).
  • this method requires a relatively high reaction temperature of 300 ° C., which is not sufficient from the viewpoint of economical desulfurization.
  • the life of the desulfurizing agent to be used is not sufficient, there is a problem that the period until the activity recovery treatment with hydrogen or the replacement with a new desulfurizing agent is relatively short.
  • this invention makes it a subject to provide the desulfurization agent which can desulfurize hydrocarbon oil stably over a long term under specific conditions, and its manufacturing method.
  • the present inventors can stably reduce the sulfur content for a long period of time by treating hydrocarbon oil with a specific desulfurizing agent under specific conditions, The inventors have found that such a desulfurizing agent can be produced with good productivity by a specific method, and have arrived at the present invention.
  • the present invention (1) A method for producing a desulfurization agent, wherein an alkaline solution and an acidic solution containing nickel and zinc are simultaneously dropped into water to form a precipitate. (2) The method for producing a desulfurization agent according to (1), wherein nickel sulfate is used as a nickel raw material and zinc sulfate is used as a zinc raw material.
  • desulfurization of hydrocarbon oil can be carried out stably and economically over a long period of time.
  • Such a desulfurizing agent can be produced with good productivity by the method for producing a desulfurizing agent of the present invention.
  • the desulfurization agent of the present invention contains nickel and zinc, and can be obtained by, for example, precipitating metal components such as zinc and nickel by a coprecipitation method, filtering, washing, molding, and firing. it can.
  • the nickel content relative to the total mass of the desulfurizing agent is preferably 1 to 30% by mass, more preferably 3 to 24% by mass, and particularly preferably 5 to 20% by mass.
  • the zinc content with respect to the total mass of the desulfurizing agent is preferably 30 to 80% by mass, more preferably 40 to 75% by mass, and particularly preferably 45 to 70% by mass.
  • the life of the desulfurizing agent is long, and when the nickel content is 20% by mass or less and the zinc content is 45% by mass or more. In particular, the life of the desulfurizing agent is prolonged.
  • the total content of nickel and zinc is preferably in the range of 35 to 85% by mass, particularly 50 to 85% by mass with respect to the total mass of the desulfurizing agent.
  • the desulfurization agent of the present invention contains nickel and zinc as oxides and may further contain elements other than nickel, zinc and oxygen, but from the viewpoint of the life of the desulfurization agent, the inclusion of elements other than nickel, zinc and oxygen A smaller amount is preferred. Therefore, in the desulfurization agent of the present invention, the total content of nickel oxide (NiO) and zinc oxide (ZnO) is preferably 90% by mass or more, more preferably 94% by mass or more, further preferably based on the total mass of the desulfurization agent. Preferably it is 96 mass% or more, Most preferably, it is 99 mass% or more.
  • the mass ratio of zinc atoms to nickel atoms (Zn / Ni) in the desulfurizing agent is preferably in the range of 1 to 15, more preferably in the range of 3 to 12, and particularly preferably in the range of 3 to 8.
  • the mass ratio of zinc atom to nickel atom (Zn / Ni) is less than 1, the life of the desulfurizing agent is remarkably shortened, and when it exceeds 15, the life of the desulfurizing agent is shortened.
  • the crystallite diameter (X) of nickel oxide is 5.0 nm or less, preferably 4.5 nm or less, more preferably 3.0 nm or less
  • the crystallite diameter of zinc oxide ( Y) is 15 nm or less, preferably 12 nm or less, more preferably 10 nm or less, and particularly preferably 8 nm or less.
  • the crystallite diameter of nickel oxide exceeds 5.0 nm, the contact efficiency between nickel and hydrocarbon oil is reduced, and the ability to take in sulfur is reduced.
  • the crystallite diameter of zinc oxide is 15 nm. If it exceeds 1, zinc oxide is not preferable because the efficiency of fixing sulfur decreases.
  • the ratio (Y / X) of the crystallite diameter (Y) of the zinc oxide and the crystallite diameter (X) of the nickel oxide is preferably 2 or more, and more preferably 2.5 or more.
  • the ratio of the crystallite diameter of zinc oxide to the crystallite diameter of nickel oxide is less than 2, the contact efficiency between nickel and hydrocarbon oil decreases, and the sulfur compound in the hydrocarbon oil is taken into the desulfurization agent. At the same time as the ability is reduced, the efficiency with which zinc fixes sulfur is reduced.
  • the desulfurization agent of the present invention has a total pore volume (V1) of 0.35 to 1.00 mL / g, preferably 0.45 to 1.00 mL / g, more preferably 0.50 to 1.00 mL / g, Particularly preferred is 0.60 to 1.00 mL / g. If the total pore volume of the desulfurizing agent is less than 0.35 mL / g, the space in which the desulfurization reaction occurs mainly decreases, which is not preferable. On the other hand, if it exceeds 1.00 mL / g, the bulk density of the desulfurizing agent is reduced, and the mass that can be charged into a reactor having a constant capacity is reduced, which is not preferable.
  • the desulfurization agent of the present invention preferably has a pore volume (V2) having a pore diameter of 2 to 30 nm of 0.08 to 0.50 mL / g, more preferably 0.15 to 0.40 mL / g, and particularly preferably. Is 0.20 to 0.30 mL / g. If the volume of the pores having a pore diameter of 2 to 30 nm is less than 0.08 mL / g, the space in which the desulfurization reaction occurs mainly decreases, which is not preferable.
  • the volume of the pores having a pore diameter of 2 to 30 nm exceeds 0.50 mL / g, the bulk density of the desulfurizing agent is reduced, and the mass that can be charged in a reactor with a constant volume is reduced, resulting in a shorter life. Absent.
  • the ratio (V2 / V1) of the pore volume (V2) having a pore diameter of 2 to 30 nm with respect to the total pore volume (V1) is preferably 0.15 to 1.00. It is preferably 0.30 to 0.60.
  • the ratio (V2 / V1) is less than 0.15, the contact efficiency between the hydrocarbon oil and nickel in the pores deteriorates, or sufficient strength is obtained when the desulfurizing agent is used industrially. It is not preferable because it disappears.
  • the ratio (V2 / V1) is 0.60 or less, preferable contact efficiency can be obtained by an appropriate combination of pores having a large diameter and small pores.
  • the desulfurizing agent of the present invention has a specific surface area of 70 m 2 / g or more, preferably 75 m 2 / g or more, more preferably 90 m 2 / g or more.
  • a specific surface area is 200 m ⁇ 2 > / g or less, Preferably it is 170 m ⁇ 2 > / g or less, More preferably, it is 150 m ⁇ 2 > / g or less.
  • the specific surface area of the desulfurizing agent exceeds 200 m 2 / g, the bulk density of the desulfurizing agent is reduced, and the mass that can be charged in a reactor having a certain capacity is reduced, which is not preferable.
  • the desulfurizing agent of the present invention is preferably used after being treated at 200 to 350 ° C., particularly 250 to 300 ° C. in a hydrogen atmosphere.
  • a treatment temperature under a hydrogen atmosphere of less than 200 ° C. is not preferable because nickel is not reduced.
  • the treatment temperature exceeds 350 ° C., nickel is sintered and the activity is lowered, which is not preferable.
  • the desulfurizing agent of the present invention is preferably prepared by a coprecipitation method.
  • the preparation method by coprecipitation method contains more nickel and zinc effective for desulfurization in the desulfurization agent than the production method in which a porous carrier such as alumina is impregnated with metal components such as zinc and nickel, and is fired. Therefore, the life of the desulfurizing agent can be extended.
  • the method of impregnating the zinc oxide support with nickel is not preferable because the specific surface area and the pore volume are reduced due to the blockage of the pores of the zinc oxide support and the desulfurization activity is lowered.
  • the desulfurization agent of the present invention is particularly preferably prepared by simultaneously dropping an acidic solution and an alkaline solution containing nickel and zinc into water to produce a precipitate containing nickel and zinc.
  • the water used preferably has a pH of 6.0 to 8.0.
  • the simultaneous dropping of the acidic solution and the alkaline solution means that the acidic solution is dropped while the acidic solution is dropped for a period of 80% by volume or more, preferably 90% by volume or more. It means that the acidic solution is being dropped while the alkaline solution is being dropped while the solution is being dropped and the amount of 80% by volume or more, preferably 90% by volume or more of the alkaline solution is being dropped.
  • the acidic solution containing nickel and zinc is obtained by dissolving zinc, nickel sulfate, nitrate, acetate, etc. with water, and the pH is preferably 5.0 or less, more preferably 4.5 or less. Yes, particularly preferably 4.0 or less, preferably 0.5 or more, more preferably 2.0 or more. If the pH of the acidic solution exceeds 5.0, it is not preferable because the nucleation rate in the solution becomes slow and the crystal grows easily, and the degree of dispersion of nickel and zinc becomes low.
  • the pH of the acidic solution is too low, particularly less than 0.5, the amount of the coprecipitation solution is small, the viscosity is high and stirring is difficult, and it is difficult to obtain a uniform physical property, which is not preferable.
  • the total concentration of nickel and zinc in the acidic solution is preferably in the range of 0.3 to 3.0 mol / L, and more preferably in the range of 0.3 to 1.0 mol / L.
  • the dropping amount of the acidic solution is preferably in the range of 0.3 to 4.0 L with respect to 1 L of water, and more preferably in the range of 1.0 to 3.5 L.
  • the acid solution is preferably prepared using nickel sulfate as the nickel raw material and zinc sulfate as the zinc raw material.
  • the specific surface area of the desulfurizing agent is increased by preparing the desulfurizing agent using nickel sulfate as the nickel raw material and zinc sulfate as the zinc raw material.
  • the crystallite diameter of the nickel oxide and the crystallite diameter of the zinc oxide Can be reduced.
  • the nickel sulfate and zinc sulfate used as raw materials may be hydrates or anhydrides.
  • sodium carbonate, ammonium carbonate, or the like can be used for the alkaline solution, and sodium carbonate is preferably used.
  • the pH of the alkaline solution is preferably 11-13.
  • the cation concentration in the alkaline solution is preferably in the range of 0.3 to 4.0 mol / L, and more preferably in the range of 0.3 to 1.5 mol / L.
  • examples of the cation in the alkaline solution include sodium ion and ammonium ion.
  • the crystallite diameter of nickel oxide and the crystallite diameter of zinc oxide can be made sufficiently small by setting the cation concentration in the alkaline solution to 4.0 mol / L or less.
  • the productivity of the desulfurizing agent is lowered.
  • the dropping amount of the alkaline solution is preferably in the range of 0.3 to 4.0 L with respect to 1 L of water, and more preferably in the range of 1.0 to 3.5 L.
  • the pH during coprecipitation is preferably 7.0 to 9.0. If the pH during coprecipitation is less than 7.0, a part of nickel does not precipitate, which is not preferable. On the other hand, if the pH during coprecipitation exceeds 9.0, an alkaline component tends to remain in the precipitation, which is not preferable. Moreover, after dropping the acidic solution and the alkaline solution into water, it is desirable to continuously stir for 1 hour or more. Further, the liquid temperature at the time of coprecipitation is preferably in the range of 50 to 70 ° C. from the viewpoint of the solubility of the alkali component.
  • the precipitate generated in the above step needs to be dried after filtration, but the drying temperature is preferably 100 to 200 ° C. Further, the temperature in the subsequent firing is preferably 300 to 400 ° C., more preferably 300 to 350 ° C. A calcination temperature of less than 300 ° C. is not preferable because the salt is not completely decomposed when the nickel and zinc components are precipitated. On the other hand, if the firing temperature exceeds 400 ° C., crystallization of nickel and zinc oxide formed by decomposition of the salt proceeds, and the degree of dispersion of nickel with respect to zinc is lowered, which is not preferable.
  • the desulfurizing agent refers to a desulfurizing agent having a sulfur sorption function.
  • the desulfurization agent having a sulfur sorption function here is to fix the sulfur atom in the organic sulfur compound to the desulfurization agent, and for hydrocarbon residues other than the sulfur atom in the organic sulfur compound in the organic sulfur compound.
  • the hydrocarbon compound from which the sulfur atom is removed may be further subjected to a reaction such as hydrogenation, isomerization, or decomposition to become another compound.
  • a reaction such as hydrogenation, isomerization, or decomposition to become another compound.
  • sulfur since sulfur is fixed to the desulfurizing agent, unlike a hydrorefining treatment, sulfur compounds such as hydrogen sulfide are not generated as a product. This eliminates the need for equipment for removing hydrogen sulfide, which is economically advantageous.
  • the raw material hydrocarbon oil to be subjected to the desulfurization method according to the present invention is not particularly limited as long as it is a hydrocarbon oil containing a sulfur content, but preferably contains 2 ppm by mass or more of sulfur content, more preferably 2 to 1, 000 ppm by mass, more preferably 2 to 100 ppm by mass, particularly preferably 2 to 40 ppm by mass.
  • sulfur content exceeds 1,000 ppm by mass, the life of the desulfurizing agent is shortened, which is not preferable.
  • the hydrocarbon oil as a raw material include base materials corresponding to LPG fraction, gasoline fraction, naphtha fraction, kerosene fraction, light oil fraction, etc. that are generally produced in refineries and the like.
  • the LPG fraction is a fuel gas mainly composed of propane, propylene, butane, butylene, and industrial raw material gas.
  • the LPG fraction is usually stored in a liquid phase in a spherical tank under pressure as called LPG (liquefied petroleum gas) or at a low temperature near atmospheric pressure. Stored in state.
  • LPG liquefied petroleum gas
  • the gasoline fraction is generally composed mainly of hydrocarbons having 4 to 11 carbon atoms, the density (15 ° C.) is 0.783 g / cm 3 or less, the 10% distillation temperature is 24 ° C.
  • the naphtha fraction is composed of gasoline fraction components (hole naphtha, light naphtha, heavy naphtha, or hydrodesulfurized naphtha thereof) or a raw material for catalytic reforming (desulfurized heavy naphtha) for producing a gasoline base.
  • the boiling point range is almost the same as that of the gasoline fraction or it is included in the boiling range of the gasoline fraction. Therefore, it is often used in the same meaning as the gasoline fraction.
  • the kerosene fraction is generally a hydrocarbon mixture having a boiling range of 150 to 280 ° C.
  • the gas oil fraction is generally a hydrocarbon mixture having a boiling range of 190 to 350 ° C.
  • the hydrocarbon oil as a raw material is not limited to those produced at refineries and the like, but contains 2 to 1,000 mass ppm of sulfur, petroleum (hydrocarbon) gas produced from petrochemical, A fraction having a similar boiling range may be used.
  • hydrocarbon oils that can be preferably used include those obtained by further fractionating hydrocarbons obtained by pyrolysis or catalytic cracking of heavy oils.
  • hydrocarbon oil as the raw material to be subjected to the desulfurization method according to the present invention is catalytic cracked gasoline and light oil fraction. Since catalytically cracked gasoline contains a large amount of olefins, hydrorefining with a hydrodesulfurization catalyst that is generally performed hydrogenates the olefin content and greatly reduces the octane number. However, in the desulfurization method of the present invention, almost no olefin content is present. Not hydrogenated. In addition, since the gas oil fraction contains a large amount of aromatics, the amount of hydrogen consumed is large because the aromatics are hydrogenated in the hydrorefining using a hydrodesulfurization catalyst that is generally performed.
  • the aromatic content is hardly hydrogenated.
  • the sulfur content is usually about 10,000 mass ppm
  • the sulfur content was reduced to some extent by hydrorefining with a hydrodesulfurization catalyst, specifically about 5 to 50 mass ppm. Thereafter, it is preferable to apply the desulfurization method of the present invention. When there is much sulfur content, the lifetime of a desulfurization agent will fall large.
  • the reaction temperature is 50 to 300 ° C., preferably 100 to 300 ° C.
  • the reaction temperature is less than 50 ° C.
  • the desulfurization rate decreases, and it is not preferable because desulfurization cannot be efficiently performed.
  • the reaction temperature exceeds 300 ° C.
  • the desulfurizing agent is sintered, and both the desulfurization rate and the desulfurization capacity are lowered, which is not preferable. If the reaction temperature is 100 ° C. or higher, the desulfurization rate is sufficiently high and desulfurization can be performed efficiently.
  • the reaction pressure is 0.2 to 5.0 MPa in gauge pressure, preferably 0.2 to 3.0 MPa, particularly preferably 0.2 to 2.0 MPa.
  • the reaction pressure is less than 0.2 MPa, the desulfurization rate decreases, and it is not preferable because desulfurization cannot be efficiently performed.
  • the reaction pressure exceeds 5.0 MPa, side reactions such as hydrogenation of olefins and aromatics contained in the hydrocarbon oil proceed, which is not preferable. If the reaction pressure is 3.0 MPa or less, side reactions such as hydrogenation of olefins and aromatics can be sufficiently suppressed, and if it is 2.0 MPa or less, these side reactions can be reliably prevented.
  • the liquid hourly space velocity exceeds 2.0 h ⁇ 1 , preferably 2.1 h ⁇ 1 or more.
  • the LHSV is preferably 50.0 h ⁇ 1 or less, more preferably 20.0 h ⁇ 1 or less, and even more preferably 10.0 h ⁇ 1 or less. If the LHSV is 2.0 h ⁇ 1 or less, the amount of oil passing is limited or the desulfurization reactor becomes too large, so it is not preferable because it cannot economically desulfurize. On the other hand, if LHSV exceeds 50.0 h ⁇ 1 , a contact time sufficient for desulfurization cannot be obtained, and the desulfurization rate decreases, which is not preferable.
  • LHSV is 2.1 h ⁇ 1 or more
  • desulfurization can be performed sufficiently economically, and if LHSV is 20.0 h ⁇ 1 or less, the contact time is sufficiently long, so that the desulfurization rate is improved. If it is 10.0 h ⁇ 1 or less, the desulfurization rate is particularly high.
  • the hydrogen / oil ratio is not particularly limited, but is preferably 0.01 to 200 NL / L, more preferably 0.01 to 100 NL / L, and more preferably 0.1 to 100 NL for a fraction containing a large amount of olefins such as catalytic cracked gasoline. / L is particularly preferred. If the hydrogen / oil ratio is less than 0.01 NL / L, desulfurization does not proceed sufficiently, which is not preferable. On the other hand, when the hydrogen / oil ratio exceeds 200 NL / L, the ratio of side reactions such as hydrogenation of olefins increases, which is not preferable.
  • the hydrogen / oil ratio is preferably 1 to 1000 NL / L, more preferably 10 to 500 NL / L, and particularly preferably 50 to 400 NL / L.
  • the hydrogen / oil ratio is less than 1 NL / L, desulfurization does not proceed sufficiently, which is not preferable.
  • the hydrogen / oil ratio exceeds 1000 NL / L, the hydrogen flow rate becomes too high, and the hydrogen compressor becomes undesirably large.
  • the hydrogen used may contain impurities such as methane, but the hydrogen purity is preferably 50% by volume or more, more preferably 80% by volume or more, and particularly 95% by volume or more so that the hydrogen compressor does not become too large. preferable. If the sulfur compound such as hydrogen sulfide is contained in the hydrogen, the life of the desulfurizing agent is shortened. Therefore, the sulfur content in the hydrogen is preferably 1,000 ppm by volume or less, more preferably 100 ppm by volume or less, especially 10 ppm. A capacity of ppm or less is preferred.
  • the resulting precipitate was filtered and washed with water. Then, after drying at 120 degreeC for 16 hours, it baked at 350 degreeC for 3 hours, and obtained the desulfurization agent (I).
  • the desulfurizing agent (I) has a nickel content of 17.3% by mass, a zinc content of 59.5% by mass and a sodium content of 0.01% by mass, and the ratio of the nickel content to the zinc content (mass ) Was 0.29.
  • the ratio of the crystallite diameter of zinc oxide to that of nickel oxide was 2.4.
  • the metal content was measured by the alkali melting ICP method, the crystallite diameter of the oxide was measured by XRD, and the pore volume was measured by the BJH method by nitrogen adsorption / desorption method.
  • the reactor was filled with the desulfurizing agent (I), subjected to reduction treatment at 300 ° C. for 16 hours in a hydrogen stream, and then an oil passage test for hydrocarbon oil was performed.
  • hydrocarbon oil heavy catalytic cracked gasoline having a sulfur content of 13 mass ppm was used.
  • hydrocarbon oil was started to flow from the reactor inlet.
  • the time (cycle length) for maintaining the desulfurization rate of 50% or more was 400 hours.
  • the sulfur content was measured based on ASTM D 5453 (ultraviolet fluorescence method).
  • Example 1 An acidic solution A having a pH of 2.6 (total concentration of nickel and zinc: 2.7 mol / L) in which 178.5 g of zinc nitrate hexahydrate and 58.2 g of nickel nitrate hexahydrate were dissolved in 300 mL of water was prepared. Further, an alkaline solution B (sodium ion concentration: 3.3 mol / L) having a pH of 12.0 in which 104 g of sodium carbonate was dissolved in 300 mL of water was prepared.
  • the acidic solution A and alkaline solution B prepared above were added dropwise while stirring 600 mL of distilled water having a pH of 7.0 at a temperature of 60 ° C.
  • the acidic solution A and the alkaline solution B started dripping almost simultaneously, and the dripping was completed in 60 minutes. Thereafter, stirring was continued for 1 hour.
  • the pH after dropping all was 8.2 at a temperature of 28 ° C.
  • the resulting precipitate was filtered and washed with water. Then, after drying at 120 ° C. for 16 hours, calcination was performed at 350 ° C. for 3 hours to obtain a desulfurization agent (II).
  • Example 2 The amount of water when preparing the acidic solution A is 1,000 mL (pH 3.2, the total concentration of nickel and zinc: 0.8 mol / L), and the amount of water when preparing the alkaline solution B is 1,000 mL.
  • a desulfurizing agent (III) was obtained in the same manner as in Example 1 except that the pH was adjusted to 11.4 and the sodium ion concentration was 1.0 mol / L. Further, in the same manner as in Comparative Example 1, an oil passage test of hydrocarbon oil was performed. The results are shown in Table 1.
  • Example 3 The amount of water when preparing the acidic solution A is 2,000 mL (pH 3.6, total concentration of nickel and zinc: 0.4 mol / L), and the amount of water when preparing the alkaline solution B is 2,000 mL.
  • a desulfurizing agent (IV) was obtained in the same manner as in Example 1 except that the pH was adjusted to 11.3 and the sodium ion concentration was 0.5 mol / L. Further, in the same manner as in Comparative Example 1, an oil passage test of hydrocarbon oil was performed. The results are shown in Table 1.
  • Example 4 An acidic solution A was prepared by changing the nitrate of Example 1 to a sulfate. Specifically, 172.5 g of zinc sulfate heptahydrate and 52.6 g of nickel sulfate hexahydrate were dissolved in 300 mL of water, and sulfuric acid was added dropwise to add acid solution A having a pH of 1.6 (total concentration of nickel and zinc). : 2.7 mol / L). Further, an alkaline solution B (sodium ion concentration: 3.3 mol / L) having a pH of 12.0 in which 104 g of sodium carbonate was dissolved in 300 mL of water was prepared.
  • an alkaline solution B sodium ion concentration: 3.3 mol / L having a pH of 12.0 in which 104 g of sodium carbonate was dissolved in 300 mL of water was prepared.
  • the acidic solution A and alkaline solution B prepared above were added dropwise while stirring 600 mL of distilled water having a pH of 7.0 at a temperature of 60 ° C.
  • the acidic solution A and the alkaline solution B started dripping almost simultaneously, and the dripping was completed in 60 minutes. Thereafter, stirring was continued for 1 hour.
  • the pH after dropping all was 8.2 at a temperature of 28 ° C.
  • the resulting precipitate was filtered and washed with water. Then, after drying at 120 degreeC for 16 hours, it baked at 350 degreeC for 3 hours, and obtained the desulfurization agent (V).
  • Example 5 The amount of water in the acidic solution A is 1,000 mL (pH 2.3, the total concentration of nickel and zinc: 0.8 mol / L), and the amount of water in the alkaline solution B is 1,000 mL (pH 11.4, sodium ion concentration).
  • the desulfurizing agent (VI) was obtained in the same manner as in Example 4 except that the amount was 1.0 mol / L). Further, in the same manner as in Comparative Example 1, an oil passage test of hydrocarbon oil was performed. The results are shown in Table 1.
  • Example 6 The amount of water in the acidic solution A is 2,000 mL (pH 4.3, total concentration of nickel and zinc: 0.4 mol / L), and the amount of water in the alkaline solution B is 2,000 mL (pH 11.3, sodium ion concentration). : 0.5 mol / L), a desulfurization agent (VII) was obtained in the same manner as in Example 4. Further, in the same manner as in Comparative Example 1, an oil passage test of hydrocarbon oil was performed. The results are shown in Table 1.
  • Example 7 The amount of water in the acidic solution A is 1,000 mL (pH 4.8, the total concentration of nickel and zinc: 0.8 mol / L), and the amount of water in the alkaline solution B is 1,000 mL (pH 11.4, sodium ion concentration).
  • the desulfurization agent (VIII) was obtained in the same manner as in Example 4 except that the calcination was performed at 280 ° C. for 2 hours. Further, an oil passage test for hydrocarbon oil was conducted in the same manner as in Comparative Example 1 except that the reduction temperature was 250 ° C. The results are shown in Table 1.
  • the desulfurization agents of the examples according to the present invention can exhibit a sufficient desulfurization effect over a long period of time even at a reaction temperature of 140 ° C.
  • the desulfurization agent of Comparative Example 1 was prepared by adding an acidic solution to an alkaline solution to prepare a desulfurization agent, so that the crystallite diameters of nickel oxide and zinc oxide were too large, and as a result, the specific surface area was too small. The period during which the desulfurization rate can be maintained at 50% or more was short.
  • Example 1 and Example 4 and Example 2 and Example 5 the desulfurization agent prepared using nickel sulfate and zinc sulfate as raw materials was obtained by using the crystallite diameters of nickel oxide and zinc oxide. Is small, the specific surface area is large, and it can be seen that the period during which the desulfurization rate is maintained at 50% or more is long.

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

Abstract

L'invention concerne un agent désulfurant qui permet de désulfurer de manière stable et économique une huile d'hydrocarbure pendant une longue période dans des conditions spécifiques. L'invention concerne également un procédé de production de l'agent désulfurant, ce dernier se caractérisant en ce que le nickel et le zinc y sont contenus  sous forme d'oxydes, et que l'aire de surface spécifique associée est de 70-200 m2/g, que l'oxyde de nickel présente une taille de cristallite n'excédant pas 5 nm, que l'oxyde de zinc présente une taille de cristallite n'excédant pas 15 nm, et que leur volume total de pores est de  0,35-1,00 mL/g. Le procédé de production de l'agent désulfurant se caractérise en ce qu'un précipité est formé par gouttelettes simultanées d'une solution alcaline et d'une solution acide contenant du nickel et du zinc dans l'eau.
PCT/JP2009/066374 2008-09-29 2009-09-18 Agent desulfurant, son procede de production, et procede de desulfuration de l'huile d'hydrocarbure WO2010035710A1 (fr)

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JP2012030211A (ja) * 2010-08-03 2012-02-16 Japan Petroleum Energy Center 炭化水素用脱硫剤の製造方法
EP2548935A4 (fr) * 2010-03-19 2015-07-22 Japan Petroleum Energy Ct Agent de désulfuration et son procédé de fabrication
WO2024013756A1 (fr) * 2022-07-11 2024-01-18 Hindustan Petroleum Corporation Limited Procédé de préparation d'un adsorbant mésoporeux pour la désulfuration d'hydrocarbures

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JP2006312663A (ja) * 2005-05-06 2006-11-16 Japan Energy Corp 炭化水素油の脱硫方法
JP2008115309A (ja) * 2006-11-07 2008-05-22 Nippon Oil Corp 灯油用脱硫剤、脱硫方法およびそれを用いた燃料電池システム

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JP2006312663A (ja) * 2005-05-06 2006-11-16 Japan Energy Corp 炭化水素油の脱硫方法
JP2008115309A (ja) * 2006-11-07 2008-05-22 Nippon Oil Corp 灯油用脱硫剤、脱硫方法およびそれを用いた燃料電池システム

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Cited By (3)

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Publication number Priority date Publication date Assignee Title
EP2548935A4 (fr) * 2010-03-19 2015-07-22 Japan Petroleum Energy Ct Agent de désulfuration et son procédé de fabrication
JP2012030211A (ja) * 2010-08-03 2012-02-16 Japan Petroleum Energy Center 炭化水素用脱硫剤の製造方法
WO2024013756A1 (fr) * 2022-07-11 2024-01-18 Hindustan Petroleum Corporation Limited Procédé de préparation d'un adsorbant mésoporeux pour la désulfuration d'hydrocarbures

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