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US20100206770A1 - Hydrorefining method for hydrocarbon oil - Google Patents

Hydrorefining method for hydrocarbon oil Download PDF

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Publication number
US20100206770A1
US20100206770A1 US12/668,560 US66856008A US2010206770A1 US 20100206770 A1 US20100206770 A1 US 20100206770A1 US 66856008 A US66856008 A US 66856008A US 2010206770 A1 US2010206770 A1 US 2010206770A1
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Prior art keywords
oil
hydrogen
hydrocarbon oil
hydrorefining
concentration
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Inventor
Junshi Matsui
Jun Mase
Hiroshi Iida
Nobuyuki Ohta
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Idemitsu Kosan Co Ltd
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Idemitsu Kosan Co Ltd
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Assigned to IDEMITSU KOSAN CO., LTD. reassignment IDEMITSU KOSAN CO., LTD. ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: IIDA, HIROSHI, MASE, JUN, MATSUI, JUNSHI, OHTA, NOBUYUKI
Publication of US20100206770A1 publication Critical patent/US20100206770A1/en
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    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing
    • C10G45/22—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds to eliminate hetero atoms without changing the skeleton of the hydrocarbon involved and without cracking into lower boiling hydrocarbons; Hydrofinishing with hydrogen dissolved or suspended in the oil
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G45/00—Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/44—Hydrogenation of the aromatic hydrocarbons
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1033—Oil well production fluids
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1048—Middle distillates
    • C10G2300/1051—Kerosene having a boiling range of about 180 - 230 °C
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1037—Hydrocarbon fractions
    • C10G2300/1048—Middle distillates
    • C10G2300/1059—Gasoil having a boiling range of about 330 - 427 °C
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/107—Atmospheric residues having a boiling point of at least about 538 °C
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1074—Vacuum distillates
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10—Feedstock materials
    • C10G2300/1077—Vacuum residues
    • 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
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4018—Spatial velocity, e.g. LHSV, WHSV

Definitions

  • the present invention relates to a method for hydrorefining a hydrocarbon oil. More particularly, the present invention relates to a hydrocarbon oil hydrorefining method for effectively hydrorefining a heavy hydrocarbon oil contained in an oil mixture, the oil mixture containing the heavy hydrocarbon oil and a specific hydrocarbon oil.
  • a conventional crude oil refining method generally, crude oil is separated into fractions through atmospheric distillation, and then each fractions are subjected to desulfurization.
  • a method is not necessarily satisfactory, since the method poses problems in that, for example, it requires a large number of oil-refining facilities, intricate processes, and excessive energy due to repeated cooling and heating of products. Therefore, demand has arisen for a new crude oil processing method. From such viewpoints, in recent years, attempts have been made to process crude oil or naphtha-fraction-free crude oil in one batch.
  • Patent Document 1 a method in which a naphtha fraction is separated from crude oil through distillation, and the resultant naphtha-free residual oil is subjected to hydrodesulfurization all together and then separated into products through distillation
  • Patent Document 2 a method in which a naphtha fraction is separated from crude oil through distillation, and the resultant naphtha-free residual oil is subjected to hydrodesulfurization all together and then separated into a light oil fraction and a heavy oil fraction by means of a high-pressure separation vessel, followed by hydrorefining of the light oil fraction.
  • Patent Document 2 Such methods proposed above, in which an oil mixture containing two or more oil fractions is subjected to hydrotreatment, could achieve effective hydrorefining.
  • Patent Document 3 discloses a method in which residual oil is mixed with a diluent having a specific boiling point, and the mixture is subjected to desulfurization and demetallization under specific conditions. According to this method, desulfurization rate and/or demetallization rate increases, thereby effectively lowering the sulfur and/or metal content of the hydrotreated residual oil.
  • Patent Document 1 Japanese Patent Application Publication (kokai) No. H03-294390
  • Patent Document 2 Japanese Patent Application Publication (kokai) No. H04-224890
  • Patent Document 3 Japanese Patent Application Publication (kokai) No. H04-239094
  • an object of the present invention is to provide a hydrocarbon oil hydrorefining method which, in hydrorefining of a hydrocarbon oil containing heavy oil, can enhance performance in hydrorefining of the heavy oil, to thereby produce an increased amount of a refined oil, to produce a high-quality refined oil, and to attain mild hydrorefining conditions.
  • hydrodesulfurization reaction there is a difference in processing rate between a heavy hydrocarbon oil and a light hydrocarbon oil.
  • a heavy hydrocarbon oil is processed at very low efficiency, as compared with the case of a light hydrocarbon oil.
  • hydrodesulfurization reaction of the light hydrocarbon oil is completed in the vicinity of an inlet of a reactor, and, after completion of the reaction, the light hydrocarbon oil serves as an inert diluent.
  • this effect of the light hydrocarbon oil may be referred to as the “dilution effect”).
  • the hydrodesulfurization technique leaves room for improvement in terms of energy savings in the overall process of crude oil refining, since, as described above, the light hydrocarbon oil can be refined within a shorter period of time under mild conditions, as compared with the case of the heavy hydrocarbon oil.
  • the present inventors have conducted extensive studies, and as a result have found that when a specific light hydrocarbon oil is added to a heavy hydrocarbon oil, and the mixture is processed through a specific method, effects other than the aforementioned dilution effect can be obtained, and hydrorefining can be carried out more effectively.
  • the present invention has been accomplished on the basis of this finding. Accordingly, the present invention provides the following:
  • a hydrocarbon oil hydrorefining method characterized by comprising providing a mixture of a heavy hydrocarbon oil and a dissolved-hydrogen-concentration-increasing hydrocarbon oil (i.e., a hydrocarbon oil exhibiting an effect of increasing the concentration of dissolved hydrogen); mixing the oil mixture, which is subjected to hydrorefining, with hydrogen; and causing the resultant mixture to pass through a reactor for carrying out hydrorefining; (2) a hydrocarbon oil hydrorefining method as described in (1) above, wherein the oil mixture of a heavy hydrocarbon oil and a dissolved-hydrogen-concentration-increasing hydrocarbon oil has a dissolved hydrogen concentration which is 1.1 times or more the highest possible hydrogen concentration of the heavy hydrocarbon oil; (3) a hydrocarbon oil hydrorefining method as described in (1) above, wherein the heavy hydrocarbon oil is one or more species selected from among vacuum residual oil, vacuum gas oil, atmospheric residual oil, topped crude oil, crude oil, deasphalted oil, coal-liquefie
  • a hydrocarbon oil hydrorefining method which, in hydrorefining of a hydrocarbon oil containing heavy oil, can further enhance performance in hydrorefining of the heavy oil, to thereby produce an increased amount of a refined oil, to produce a high-quality refined oil, and to attain mild hydrorefining conditions.
  • the hydrorefining method comprises adding a specific light hydrocarbon oil to a heavy hydrocarbon oil, and processing the resultant mixture under specific conditions. Therefore, according to the hydrorefining method, a defect that the light hydrocarbon oil is subjected to hydrorefining for a long period of time under severe conditions is solved and the energy savings can be achieved in the overall process of crude oil.
  • FIG. 1 schematically shows a diagram of steps included in the present invention.
  • FIG. 2 schematically shows another diagram of steps included in the present invention.
  • FIG. 3 schematically shows still another diagram of steps included in the present invention.
  • FIG. 4 schematically shows yet another diagram of steps included in the present invention.
  • hydrocarbon oil hydrorefining method of the present invention hydrogen is mixed with an oil mixture containing a heavy hydrocarbon oil and a dissolved-hydrogen-concentration-increasing hydrocarbon oil, and the hydrogen-mixed oil mixture is caused to pass through a reactor for carrying out hydrorefining.
  • the heavy hydrocarbon oil may be selected from among vacuum residual oil, vacuum gas oil, atmospheric residual oil, topped crude oil, crude oil, deasphalted oil, coal-liquefied oil, oil obtained from oil sand, and oil obtained from oil shale, and these oils may be employed singly or in combination of two or more species. Since effects of the present invention are difficult to obtain when a heavy hydrocarbon oil incapable of forming a liquid phase in the reactor is employed, an appropriate heavy oil must be selected, or appropriate reaction conditions must be provided. The present invention is intended to achieve enhancement of performance in heavy hydrocarbon oil hydrorefining, which has been conventionally difficult to attain.
  • the heavy hydrocarbon oil employed in the present invention preferably contains asphaltene (as used herein, “asphaltene” refers to an n-heptane-insoluble fraction of heavy oil obtained through extraction of the heavy oil with n-heptane) in an amount of 2 mass % or more, more preferably 4 mass % or more. Even when a heavy hydrocarbon oil having an asphaltene content of less than 2 mass % is employed, the resultant refined oil exhibits no problematic features. However, employment of such a low-asphaltene-content heavy hydrocarbon oil is not preferred from the viewpoints of cost-effectiveness and energy savings, since the heavy hydrocarbon oil is relatively easily hydrogenated without application of the present invention.
  • asphaltene as used herein, “asphaltene” refers to an n-heptane-insoluble fraction of heavy oil obtained through extraction of the heavy oil with n-heptane
  • the asphaltene content of the heavy hydrocarbon oil employed in the present invention is preferably less than 15 mass %, from the viewpoint of operation of the reactor.
  • the heavy hydrocarbon oil employed in the present invention preferably contains vanadium in an amount of 10 mass ppm or more, nickel in an amount of 10 mass ppm or more, and sulfur in an amount of 0.1 mass % or more.
  • the heavy hydrocarbon oil employed is preferably pretreated as desired.
  • the hydrocarbon oil is subjected to desalting treatment so as to have a sodium chloride content of 10 mass ppm or less.
  • the hydrocarbon oil is preferably filtered with a filter (about 10 ⁇ m).
  • dissolved-hydrogen-concentration-increasing hydrocarbon oil refers to a hydrocarbon oil which has an average boiling point of 100° C. or higher, which has a density of 0.70 to 0.95 g/mL, and which exhibits the effect of increasing the dissolved hydrogen concentration of the resultant oil mixture so that the dissolved hydrogen concentration of the oil mixture as measured under the conditions (temperature and pressure) becomes higher than the highest possible hydrogen concentration of the heavy hydrocarbon oil as measured at the same conditions.
  • the amount of the hydrocarbon oil present in a liquid phase is considerably reduced, and the hydrocarbon oil tends to exhibit poor effect of increasing hydrogen concentration.
  • a hydrocarbon oil having a density higher than 0.95 g/mL tends to exhibit poor effect of increasing dissolved hydrogen concentration.
  • Specific examples of the dissolved-hydrogen-concentration-increasing hydrocarbon oil include a straight-run kerosene fraction, a straight-run light gas oil fraction, a straight-run heavy gas oil fraction, cracked oil obtained from an FCC unit, and thermally cracked oil obtained from a coker unit. These may be employed singly or in combination of two or more species.
  • the present invention may employ a non-petroleum-origin hydrocarbon.
  • a light hydrocarbon having a boiling point lower than that of the heavy hydrocarbon oil serving as a starting oil exhibits the effect of increasing the dissolved hydrogen concentration of a liquid phase in the reactor.
  • the hydrogen partial pressure in the gas phase is reduced, and the light hydrocarbon may fail to exhibit an effect of increasing dissolved hydrogen concentration.
  • the aforementioned dissolved-hydrogen-concentration-increasing hydrocarbon oil must be present in a liquid phase entirely or partially under the temperature and pressure conditions in the reactor.
  • hydrocarbon oil is entirely or partially present in the liquid phase, hydrorefining performance can be enhanced.
  • the ratio of the amount of the hydrocarbon oil present in the liquid phase to the entire amount of the hydrocarbon oil is preferably 10% or more, more preferably 20% or more.
  • the mixture of the heavy hydrocarbon oil and the dissolved-hydrogen-concentration-increasing hydrocarbon oil has a dissolved hydrogen concentration which is 1.1 times or more the highest possible hydrogen concentration of the heavy hydrocarbon oil.
  • the dissolved-hydrogen-concentration-increasing hydrocarbon oil e.g., a light hydrocarbon oil
  • the light hydrocarbon oil is fed so that the dissolved hydrogen concentration of the hydrocarbon oil mixture is elevated to more preferably 1.15 times or more, much more preferably 1.2 times or more, the highest possible hydrogen concentration of the heavy hydrocarbon oil.
  • the dissolved-hydrogen-concentration-increasing hydrocarbon oil may be selected by means of a tool which can estimate dissolved hydrogen concentration and the equilibrium of hydrogen between gas and liquid in the reactor.
  • a process simulator Pro/II ver. 6.01 (product of Invensys Process Systems) is employed.
  • a mixer and a flusher are selected from a PFD process unit.
  • Hydrogen is selected as a fluid fed through an inlet of the mixer, and the feed rate of hydrogen is input.
  • Petroleum Petroleum Assay
  • g/cm 3 density of a heavy hydrocarbon oil which is fed
  • the SRK equation (SRK01) is selected from among general thermodynamic equations, and employed for obtaining thermodynamic data [the SRK equation is one of the most commonly used thermodynamic equations in process simulators in the field of petroleum refining].
  • step (3) a light hydrocarbon oil is selected as a fluid which is fed, in addition to the heavy hydrocarbon oil, through the inlet of the mixer, and the feed rate, density, and distillation characteristics of the light hydrocarbon oil are input. Thereafter, calculation is performed in a manner similar to that described above. Comparison of the resultant data with the above-obtained data can determine a change in dissolved hydrogen concentration of the liquid phase in the reactor in the case where the light hydrocarbon oil is fed under certain conditions. Through this procedure, the dissolved hydrogen concentration of the liquid phase at the inlet of the reactor is estimated.
  • step (2) the composition and discharge rate of offgas are input, and, in step (3), the density, distillation characteristics, and recovery rate of the thus-refined oil are input.
  • the PR equation or the GS equation may be employed as a thermodynamic equation. It was previously found that when the mixture of the heavy hydrocarbon oil and the light hydrocarbon oil is caused to pass through the reactor, and an increase in dissolved hydrogen concentration of the liquid phase is determined by use of each of these three equations, there is no difference between data obtained by use of these equations. Even when the composition of offgas discharged from the outlet of the reactor is unknown, the dissolved hydrogen concentration of the liquid phase may be estimated only on the basis of parameters of the fluid fed through the inlet of the reactor.
  • the optimum mixing ratio of the heavy hydrocarbon oil to the dissolved-hydrogen-concentration-increasing hydrocarbon oil may be estimated by means of the aforementioned process simulator.
  • hydrocarbon oil hydrorefining method will next be more specifically described.
  • a hydrocarbon oil mixture is mixed with hydrogen, and then the resultant mixture is caused to pass through the reactor for carrying out hydrorefining.
  • the heavy hydrocarbon oil is mixed with the dissolved-hydrogen-concentration-increasing hydrocarbon oil (e.g., light hydrocarbon oil), to thereby prepare an oil mixture; the oil mixture is pressurized and preheated by means of a heat exchanger, and then mixed with hydrogen; the pressurized, hydrogen-mixed oil mixture is heated to a reaction temperature in a heating furnace; and the thus-heated oil mixture is fed to the reactor.
  • the dissolved-hydrogen-concentration-increasing hydrocarbon oil e.g., light hydrocarbon oil
  • Hydrorefining is carried out under, for example, the conditions of reaction temperature: 300 to 450° C., hydrogen partial pressure: 5.1 to 25.3 MPa(G), hydrogen/oil ratio: 200 to 2,000 Nm 3 /kL, and LHSV: 0.05 to 10 hr ⁇ 1 ; or the conditions of reaction temperature: 330 to 430° C., hydrogen partial pressure: 10.1 to 20.3 MPa(G), hydrogen/oil ratio: 500 to 1,000 Nm 3 /kL, and LHSV: 0.1 to 1.0 hr ⁇ 1 .
  • hydrorefining steps include a hydrodemetallization step, a hydrodesulfurization step, a hydrocracking step, a hydrodenitrogenation step, and a hydrodearomatization step.
  • the hydrotreatment step employed in the method of the present invention and the method may employ two or more of the aforementioned hydrotreatment steps.
  • the hydrodemetallization step is carried out first. In general, firstly, the hydrodemetallization step is carried out; subsequently, the hydrodenitrogenation step, the hydrocracking step, or a similar hydrotreatment step is carried out; and finally, the hydrodesulfurization step is carried out.
  • the hydrocracking step or a similar hydrotreatment step may be further carried out after the hydrodesulfurization step.
  • No particular limitation is imposed on the type of reactor employed in any of these hydrotreatment steps, and, for example, a fixed-bed, moving-bed, fluidized-bed, ebullient bed, or slurry-bed reactor may be employed.
  • the dissolved-hydrogen-concentration-increasing hydrocarbon oil may be fed, as a quenching oil, into the reactor.
  • the aforementioned hydrodemetallization step is carried out in one or more reactors after the hydrogen-mixed hydrocarbon oil mixture has been pressurized and heated.
  • the catalyst employed in the hydrodemetallization step is preferably a catalyst prepared by supporting, on a carrier (e.g., a porous inorganic oxide such as alumina, silica, silica-alumina, or sepiolite, or a natural mineral), an active metal (i.e., at least one species selected from among metals of Groups 8, 9, and 10 of the periodic table) and a promoter metal (i.e., at least one species selected from among metals of Group 6 of the periodic table).
  • a carrier e.g., a porous inorganic oxide such as alumina, silica, silica-alumina, or sepiolite, or a natural mineral
  • an active metal i.e., at least one species selected from among metals of Groups 8, 9, and 10 of the periodic table
  • a promoter metal i.e., at least one species selected from among metals of Group 6 of the periodic table.
  • the active metal content of the hydrodemetallization catalyst is preferably 2 to
  • the promoter metal content of the hydrodemetallization catalyst is preferably 0.5 to 5 mass %, more preferably 1 to 5 mass %, as reduced to metal oxide.
  • the active metal i.e., a metal of Groups 8, 9, and 10 of the periodic table
  • the promoter metal i.e., a metal of Group 6 of the periodic table
  • the amount of the catalyst employed in the hydrodemetallization step may be appropriately determined in consideration of the metal concentration of the hydrocarbon oil mixture.
  • the amount of the hydrodemetallization catalyst is preferably 10 to 50 vol. % on the basis of the total amount of the catalysts employed in all the hydrotreatment steps.
  • the hydrodemetallization step is preferably carried out under the conditions of reaction temperature: 300 to 450° C. (more preferably 330 to 430° C.), hydrogen partial pressure: 5 to 25 MPa(G) (more preferably 10 to 20 MPa(G)), hydrogen/oil ratio: 200 to 2,000 Nm 3 /kL (more preferably 500 to 1,000 Nm 3 /kL), and LHSV (liquid hourly space velocity): 0.1 to 20 hr ⁇ 1 (more preferably 0.2 to 2 hr ⁇ 1 ).
  • reaction temperature 300 to 450° C. (more preferably 330 to 430° C.)
  • hydrogen partial pressure 5 to 25 MPa(G) (more preferably 10 to 20 MPa(G))
  • hydrogen/oil ratio 200 to 2,000 Nm 3 /kL (more preferably 500 to 1,000 Nm 3 /kL)
  • LHSV liquid hourly space velocity
  • the aforementioned hydrodesulfurization step is generally carried out after the hydrodemetallization step or a similar hydrotreatment step. Therefore, when reaction temperature control is required, preferably, the reaction temperature is controlled by means of a heat exchanger, quenching hydrogen gas, or quenching oil.
  • the hydrodesulfurization step is carried out in one or more reactors.
  • the catalyst employed in the hydrodesulfurization step may be a hydrodesulfurization catalyst generally used for heavy oil; for example, a catalyst prepared by supporting, on a carrier (e.g., alumina, silica, silica-alumina, zeolite, or a mixture thereof), at least one species selected from among metals of Groups 5, 6, 8, 9, and 10 of the periodic table.
  • a carrier e.g., alumina, silica, silica-alumina, zeolite, or a mixture thereof
  • the carrier preferably has an average pore size of 8 nm or more, and the supported metal content of the hydrodesulfurization catalyst is preferably 3 to 30 mass % as reduced to metal oxide.
  • the hydrodesulfurization step is preferably carried out under the conditions of reaction temperature: 300 to 450° C. (more preferably 330 to 430° C.), hydrogen partial pressure: 5 to 25 MPa(G) (more preferably 10 to 20 MPa(G)), hydrogen/oil ratio: 200 to 2,000 Nm 3 /kL (more preferably 500 to 1,000 Nm 3 /kL), and LHSV (liquid hourly space velocity): 0.1 to 20 hr ⁇ 1 (more preferably 0.2 to 2 hr ⁇ 1 ).
  • reaction temperature, hydrogen partial pressure, and hydrogen/oil ratio are below the above ranges, reaction efficiency tends to lower, whereas when reaction temperature, hydrogen partial pressure, and hydrogen/oil ratio exceed the above ranges, production cost tends to increase.
  • LHSV is below the above range, production cost tends to increase, whereas when LHSV exceeds the above range, reaction efficiency tends to lower.
  • the aforementioned hydrocracking step is generally carried out after the hydrodemetallization step or a similar hydrotreatment step. Therefore, when reaction temperature control is required, preferably, the reaction temperature is controlled by means of a heat exchanger, hydrogen-quenching, or oil-quenching.
  • the hydrocracking step is carried out in one or more reactors.
  • the catalyst employed in the hydrocracking step is preferably a catalyst prepared by supporting, on a carrier made of a mixture of iron-containing aluminosilicate and alumina, a metal having hydrogenation activity (i.e., at least one species selected from among metals of Groups 6, 8, 9, and 10 of the periodic table).
  • the metal of Group 6 of the periodic table is preferably tungsten or molybdenum.
  • a plurality of metals may be employed in combination.
  • a combination of nickel-molybdenum, cobalt-molybdenum, nickel-tungsten, or nickel-cobalt-molybdenum is employed, from the viewpoints of high hydrogenation activity and low degradation.
  • the hydrocracking step is preferably carried out under the conditions of reaction temperature: 300 to 450° C. (more preferably 380 to 420° C.), hydrogen partial pressure: 5 to 25 MPa(G) (more preferably 10 to 20 MPa(G)), hydrogen/oil ratio: 200 to 2,000 Nm 3 /kL (more preferably 500 to 1,000 Nm 3 /kL), and LHSV (liquid hourly space velocity): 0.1 to 20 hr ⁇ 1 (more preferably 0.2 to 2 hr ⁇ 1 ).
  • reaction temperature, hydrogen partial pressure, and hydrogen/oil ratio are below the above ranges, reaction efficiency tends to lower, whereas when reaction temperature, hydrogen partial pressure, and hydrogen/oil ratio exceed the above ranges, production cost tends to increase.
  • LHSV is below the above range, production cost tends to increase, whereas when LHSV exceeds the above range, reaction efficiency tends to lower.
  • the aforementioned hydrodenitrogenation step is carried out before the hydrocracking step.
  • the hydrodenitrogenation step is carried out in one or more reactors.
  • the hydrodenitrogenation step may be carried out through a conventionally known method; for example, the method disclosed in Japanese Patent Application Publication (kokai) No. 2003-049175.
  • the aforementioned hydrodearomatization step is carried out for the purpose of obtaining a lubricating oil base from a refined oil produced through the aforementioned hydrorefining steps.
  • the hydrodearomatization step is carried out in one or more reactors.
  • the hydrodearomatization step is preferably carried out under the conditions of reaction temperature: 300 to 450° C. (more preferably 380 to 420° C.), hydrogen partial pressure: 10 to 25 MPa(G) (more preferably 15 to 23 MPa(G)), hydrogen/oil ratio: 200 to 2,000 Nm 3 /kL, and LHSV (liquid hourly space velocity): 0.1 to 20 hr ⁇ 1 (more preferably 0.2 to 2 hr ⁇ 1 ).
  • reaction efficiency tends to lower, whereas when reaction temperature, hydrogen partial pressure, and hydrogen/oil ratio exceed the above ranges, production cost tends to increase.
  • LHSV is below the above range, production cost tends to increase, whereas when LHSV exceeds the above range, reaction efficiency tends to lower.
  • the above-hydrorefined oil is introduced to a separation step according to a customary method, and is separated into a gas fraction and a liquid fraction through treatment by means of a plurality of separation vessels. Subsequently, hydrogen sulfide, ammonia, etc. are removed from the gas fraction, and then the gas fraction is subjected to, for example, a treatment for increasing hydrogen purity. Thereafter, the resultant gas fraction is mixed with a fresh feed gas, and then recycled to the reaction step.
  • the liquid fraction obtained through the separation step is introduced into an atmospheric separation tower (called “stripper”). Subsequently, hydrogen sulfide by-produced through desulfurization is removed, and a light oil fraction is separated from the resultant refined oil.
  • Embodiments of the hydrocarbon oil hydrorefining method of the present invention will now be described with reference to FIGS. 1 to 4 .
  • FIG. 1 shows a method in which a light hydrocarbon oil is mixed with atmospheric residual oil or vacuum residual oil, and is caused to pass through a direct desulfurization unit for the residual oil (method 1 ).
  • FIG. 2 shows a refining method (modification of method 1 ), wherein the light hydrocarbon oil is also employed as a quenching oil (method 2 ).
  • FIG. 3 shows a method in which a light hydrocarbon oil is mixed with atmospheric residual oil or vacuum residual oil, and is caused to pass through a hydrocracking unit for the residual oil (method 3 ).
  • FIG. 4 shows a method in which a light hydrocarbon oil is mixed with vacuum gas oil, and is caused to pass through a hydrocracking unit for the vacuum gas oil (method 4 ).
  • Method 4 bottom oil recycling is not necessarily carried out.
  • Method 4 (except for the hydrocracking step) can be applied to the case where a light hydrocarbon oil is mixed with vacuum gas oil, and is caused to pass through a desulfurization unit for the vacuum gas oil (i.e., a so-called indirect desulfurization unit).
  • Table 1 shows characteristics of heavy hydrocarbon oils serving as feedstock.
  • Tables 2 and 3 show characteristics of hydrocarbon oils serving as mixing oils. Data shown in the Tables were obtained through the following methods.
  • Heavy Heavy hydrocarbon Heavy hydrocarbon oil A hydrocarbon oil C Arabian heavy oil B Arabian heavy atmospheric Arabian heavy vacuum residual oil vacuum gas oil residual oil Density (g/mL) 0.9873 0.9171 1.0409 S content (wt. %) 4.41 2.94 5.54 N content (wt. ppm) 2,500 740 3,760 V content (wt. ppm) 84 0.5 152 Ni content (wt. ppm) 27 0.5> 50 n-Heptane insoluble 7.89 — — components (wt. %) Conradson's Carbon 14.1 0.33 25.2 content (wt.
  • Table 4 shows characteristics of catalysts employed in hydrorefining.
  • the alumina-boria carrier of a hydrodesulfurization catalyst (catalyst B) and the steamed iron-containing zeolite of a hydrocracking catalyst (catalyst C) were respectively prepared according to Example 1 of Japanese Patent Application Publication (kokai) No. H06-319994 and Example 1 of Japanese Patent Application Publication (kokai) No. H02-289419.
  • catalyst A 25 mL and catalyst B (75 mL) were sequentially loaded into a reaction tube, followed by hydrorefining reaction.
  • Arabian heavy atmospheric residual oil (heavy hydrocarbon oil A) shown in Table 1 was fed at an LHSV of 0.21 h ⁇ 1
  • Arabian heavy straight-run kerosene (mixing oil A) shown in Table 2 was fed so that the total LHSV of the oil mixture was regulated to 0.315 h ⁇ 1 .
  • Hydrogen partial pressure was maintained at 13.2 MPa(G); hydrogen/oil ratio was maintained at 800 Nm 3 /kL; and reaction temperature was maintained at 380° C.
  • Hydrogen was mixed with the oil mixture after the oil mixture had been heated to the aforementioned reaction temperature and before the oil mixture was caused pass through the reactor.
  • the oil mixture was caused to pass through the reactor for 1,500 hours so as to stabilize hydrogenation activity, followed by production of a refined oil.
  • the refined oil was subjected to distillation by means of a 15-stage distillation apparatus according to the method specified by ASTM D2892-84, to thereby yield fractions.
  • Table 5 shows the percent cracking, sulfur content, and metal content of an atmospheric residual oil fraction (boiling point of 343° C. or higher) of the refined oil (hereinafter, this residual oil fraction may be referred to as the “343° C.+ fraction”).
  • Example 10 The hydrorefining procedure of Example 1 was repeated, except that the feedstock and the reaction conditions were changed as shown in Table 5.
  • the temperature of a hydrodemetallization zone and a hydrodesulfurization zone was controlled to 380° C.
  • the temperature of a hydrocracking zone was controlled to 400° C.
  • Example 1 The hydrorefining procedure of Example 1 was repeated, except that hydrocarbon oils and reaction conditions were changed as shown in Table 6.
  • the temperature of a hydrodemetallization zone and a hydrodesulfurization zone was controlled to 380° C.
  • the temperature of a hydrocracking zone was controlled to 400° C.
  • “LHSV for 343° C.+ fraction” shown in Tables 5 and 6 is obtained by multiplying the total LHSV for feedstock employed in the experiment by the volume-basis amount of a fraction having a boiling point of 343° C. or higher (i.e., a 343° C.+ fraction) contained in the feedstock. Therefore, “LHSV for 343° C.+ fraction” corresponds to the substantial LHSV for 343° C.+ fraction fed into the reactor.
  • the present invention is not intended to enhance hydrorefining performance by the dilution effect, but intended to enhance performance in hydrorefining of a heavy oil fraction by the aforementioned dissolved hydrogen concentration increasing effect. Therefore, hydrorefining performance was evaluated by focusing on, for example, the sulfur content of the 343° C.+ fraction of the refined oil. Desulfurization conversion for the 343° C.+ fraction was determined by use of the following calculation formula.
  • Desulfurization conversion (%) for the 343° C.+ fraction (sulfur content of the 343° C.+ fraction of feedstock ⁇ sulfur content of the 343° C.+ fraction of the refined oil)/(sulfur content of the 343° C.+ fraction of feedstock) ⁇ 100
  • composition of a gas phase or a liquid phase at the inlet or outlet of the reactor was estimated by means of a process simulator Pro/II (ver. 6.01) (product of Invensys Process Systems) as described above.
  • Example 1 the hydrogen content of the liquid phase in the reactor is higher by 28%, as compared with the case of Comparative Example 1.
  • the reaction rate of the 343° C.+ fraction is higher, as compared with the case of Comparative Example 1, although the actual LHSV for feedstock is 1.5 times that in Comparative Example 1 (i.e., in Example 1, the reaction is carried out under more disadvantageous conditions). Therefore, in Example 1, more effective hydrorefining is achieved.
  • Comparison between data of Example 1 and Comparative Example 1 shows that the hydrogen content of the liquid phase in the reactor is correlated with the reaction rate of the 343° C.+ fraction. A tendency similar to that in Example 1 is also observed in Examples 2 to 10.
  • a hydrocarbon oil hydrorefining method which, in hydrorefining of a hydrocarbon oil containing heavy oil, can enhance performance in hydrorefining of the heavy oil, to thereby produce an increased amount of a refined oil, to produce a high-quality refined oil, and to attain mild hydrorefining conditions. According to the hydrorefining method, energy savings can be achieved in the overall process of crude oil refining.

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PT2737060T (pt) 2011-07-27 2019-06-05 Flash Therapeutics Método para a produção de partículas retrovirais úteis para transdução de células eucarióticas
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US20150210937A1 (en) * 2012-07-24 2015-07-30 Reliance Industries Limited Method for removing chlorides from hydrocarbon stream by steam stripping
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