WO2006038555A1 - Procédé de fabrication de gazole hydroraffiné, gazole hydroraffiné et composition de gazole - Google Patents

Procédé de fabrication de gazole hydroraffiné, gazole hydroraffiné et composition de gazole Download PDF

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WO2006038555A1
WO2006038555A1 PCT/JP2005/018127 JP2005018127W WO2006038555A1 WO 2006038555 A1 WO2006038555 A1 WO 2006038555A1 JP 2005018127 W JP2005018127 W JP 2005018127W WO 2006038555 A1 WO2006038555 A1 WO 2006038555A1
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oil
content
volume
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PCT/JP2005/018127
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English (en)
Japanese (ja)
Inventor
Hideshi Iki
Yukihiro Sugiura
Yuichi Tanaka
Hirofumi Konno
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Nippon Oil Corporation
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Priority to EP05788266A priority Critical patent/EP1818385A4/fr
Priority to US11/664,260 priority patent/US20080308459A1/en
Publication of WO2006038555A1 publication Critical patent/WO2006038555A1/fr

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Classifications

    • 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
    • C10G45/46—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used
    • C10G45/52—Hydrogenation of the aromatic hydrocarbons characterised by the catalyst used containing platinum group metals or compounds thereof
    • 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
    • C10G65/00—Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/02—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only
    • C10G65/12—Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural serial stages only including cracking steps and other hydrotreatment steps
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/201—Impurities
    • C10G2300/202—Heteroatoms content, i.e. S, N, O, P
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20—Characteristics of the feedstock or the products
    • C10G2300/30—Physical properties of feedstocks or products
    • C10G2300/301—Boiling range
    • 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
    • C10G2400/00—Products obtained by processes covered by groups C10G9/00 - C10G69/14
    • C10G2400/06—Gasoil

Definitions

  • the present invention relates to a method for producing hydrorefined gas oil, a hydrorefined gas oil, and a gas oil composition.
  • Diesel engines are expected to play an effective role in reducing carbon dioxide emissions as a measure against global warming because of their high energy efficiency.
  • the demand for cleanliness of diesel engine exhaust gas is becoming stricter, and removal of harmful substances such as particulate components called NOx and NOx is one of the major issues.
  • the installation of exhaust gas purification devices such as particulate removal filters is increasingly being promoted.
  • Petroleum gas oil fractions usually contain 1 to 3% by mass of sulfur in an unrefined state, and are used as a gas oil base material after hydrodesulfurization.
  • Other diesel oil bases include hydrodesulfurized kerosene fractions, cracked light oil obtained from fluid catalytic cracking equipment, hydrocracking equipment, etc., and product light oil can be obtained after mixing these light oil bases .
  • sulfur compounds present in the gas oil fraction after hydrodesulfurization treatment using a hydrodesulfurization catalyst it has multiple methyl groups represented by 4,6-dimethyldibenzothiophene as substituents. Dibenzothiophene derivatives are extremely poor in reactivity.
  • an unrefined petroleum gas oil fraction usually contains 20 to 40% by volume of aromatics.
  • aromatic saturated hydrocarbons which are aromatic hydrides on the high temperature side and aromatic ring hydrides on the low temperature side, respectively.
  • reaction rate of the aromatic hydrogenation reaction is not sufficient at a relatively low reaction temperature, reaction conditions and catalysts other than the reaction temperature are necessary to compensate for the reaction rate.
  • the hydrodesulfurization reaction is a reaction that ultimately cleaves the carbon-sulfur bond, and the higher the temperature, the more the opening reaction is promoted. Therefore, in the conventional technology, if the reaction conditions are set on the low temperature side in order to promote the hydrogenation of aromatics, the desulfurization activity is insufficient, and it is extremely difficult to achieve both ultra-low sulfur and low aromaticity. It becomes difficult.
  • the effect of reducing both the sulfur content and the aromatic content is not sufficient. More specifically, even in the production methods described in these patent documents, the sulfur content is not more than ⁇ ppm by mass, and the aromatic content is not more than 1% by volume. It is difficult to achieve dearomatic levels at the same time.
  • a conventional manufacturing method if the operation severity in the first step is increased, it becomes difficult to continue the operation in the first step for a period that can be economically satisfied.
  • an increase in the reaction temperature in the first step increases the aromatic content in the product oil in the first step, thereby inhibiting dearomatization in the second step.
  • there is a limit to the increase in operating severity such as an increase in reaction temperature.
  • Patent Document 3 as a technology for converting naphthene to paraffin, a gas oil fraction is processed in a gas-liquid countercurrent process using a catalyst in which Pt is supported on USY (ultra-stabilized Y zeolite). A method is disclosed.
  • a high reaction temperature is required, and as the reaction temperature increases and the severity of the reaction conditions increases, the light oil fraction produced It tends to decrease the yield of.
  • Patent Document 1 JP-A-7-155610
  • Patent Document 2 JP-A-8-283747
  • Patent Document 3 Japanese Translation of Special Publication 2003-502478
  • the present invention has been made in view of the above circumstances, and has a sulfur content of 1 mass ppm or less, a total aromatic content of 3 vol% or less, and a high cetane number.
  • a method for producing hydrorefined diesel oil that can produce diesel oil with excellent environmental characteristics and combustion characteristics, both efficiently and reliably without special operating conditions and capital investment. The purpose is to provide. Furthermore, the present invention provides such hydrorefining. It is an object of the present invention to provide a hydrorefined light oil obtained by a method for producing light oil and a light oil composition containing the hydrorefined light oil.
  • the present invention is a method for producing a hydrorefined gas oil by hydrotreating a feedstock oil, comprising 95% by volume or more of a petroleum fraction having a boiling point range of 150 to 380 ° C as a feedstock oil.
  • a hydrorefined oil having a sulfur content of 2-15 mass ppm, a total aromatic content of 10-25% by volume, and a total naphthene content of 20-60% by volume.
  • the first step of obtaining a first product oil having a total aromatic content of 3% by volume or less by hydrotreating the raw material oil in the presence of the first hydrogenated catalyst and the crystalline molecular sieve component The first product oil is hydrotreated in the presence of the second hydrogenated catalyst contained, and the following conditions (1) and (2): (1) Boiling range force S
  • the total content of aromatics and total naphthenes is the sum of total aromatics and total naphthenes in the feedstock.
  • the method for producing hydrorefined gas oil of the present invention uses a petroleum fraction that satisfies the above-mentioned properties at the same time as a feedstock, and feeds the feed oil so as to obtain a first product oil having the above-mentioned properties in the first step.
  • the first product oil is hydrotreated so that the obtained second product oil satisfies the above conditions at the same time using the specific catalyst.
  • the environmental characteristics are such that the sulfur content is 1 mass ppm or less, the total aromatic content is 3 vol% or less, and the strength is also high cetane number.
  • light oil excellent in both combustion characteristics can be produced with sufficient efficiency and reliability without using special operating conditions and capital investment, that is, using conventional equipment.
  • the polycyclic aromatic content in the feedstock is 1 to 7% by volume, and the polycyclic aromatic content in the second product oil is 0.2% or less by volume is preferable.
  • “polycycle” includes both condensed and ring assemblies.
  • the total of the polycyclic aromatic content and the polycyclic naphthene content in the second product oil is preferably 13% by volume or less. As a result, the cetane number of the resulting hydrorefined gas oil is further improved, and better fuel characteristics can be obtained.
  • the method for producing a hydrotreated gas oil of the present invention in a first step, the reaction temperature one hundred seventy to thirty-two 0 ° C, a hydrogen partial pressure 2 to 10 MPa, liquid hourly space velocity 0. l ⁇ 4h _1 and hydrogen Z oil ratio the feedstock was hydrotreated under the reaction conditions of 250 ⁇ 800N LZL, in a second step, the reaction temperature 200 to 280 ° C, a hydrogen partial pressure 2 to 10 MPa, liquid hourly space velocity 0. l ⁇ 2h _1 and hydrogen Z oil
  • the first product oil is hydrotreated under reaction conditions of a ratio of 250-80 ONLZL. This makes it easier to obtain the first product oil or hydrorefined gas oil having the desired properties. Furthermore, shortening of catalyst life and excessive capital investment can be further suppressed.
  • both the first hydrogenation catalyst and the second hydrogenation catalyst are formed by supporting an active metal on a porous carrier, And at least one metal selected from the group consisting of Group 8 metal forces.
  • a catalyst can exhibit a more balanced desulfurization activity, aromatic hydrogenation activity, naphthene conversion activity to paraffin, etc. for achieving the object effects of the present invention.
  • the active metal is preferably at least one metal selected from the group consisting of Rh, Ir, Pd and Pt.
  • the carrier in the first hydrogenation catalyst is at least one metal oxide selected from the group consisting of titania, zircoia, polya and silica; It is preferable to contain alumina.
  • the crystalline molecular sieve component contains silica and alumina, and at least selected from the group consisting of faujasite type, beta type, mordenite type, and pentasil type force. It preferably has a single crystal structure.
  • the second hydrogenation catalyst containing such a crystalline molecular sieve component is suitable for desulfurization activity, aromatic hydrogenation activity, and conversion of naphthene to paraffin to achieve the object effects of the present invention. In particular, the conversion activity of naphthene to paraffin can be more effectively and reliably exhibited.
  • the present invention is a hydrorefining product obtained by the above-described method for producing hydrorefined light oil, having a sulfur content of 1 mass ppm or less and a total aromatic content of 3 vol% or less. Provide light oil.
  • the present invention is a hydrorefining product obtained by the above-described method for producing hydrorefined gas oil, having a sulfur content of 1 mass ppm or less and a total aromatic content of 3 vol% or less.
  • a light oil composition containing light oil is provided.
  • the method for producing hydrorefined gas oil of the present invention is a method for producing hydrorefined gas oil by hydrotreating the feedstock oil, and has a boiling range of 150 to 380 ° C as the feedstock oil.
  • the first step is to obtain a first product oil having a total aromatic content of 3% by volume or less by hydrotreating the above feed oil in the presence of the first hydrogenation catalyst using the hydrorefined oil that is And hydrotreating the first product oil in the presence of a second hydrogenation catalyst containing a crystalline molecular sieve component (1) and (2): (1) Boiling range below 150 ° C The content of petroleum fraction is 16% by volume or less; and (2) The total aromatic content and total naphthene content are the total aromatic content in the feedstock.
  • the hydrorefined oil used as the feedstock according to the present invention contains 95% by volume or more of a petroleum fraction having a boiling range of 150 to 380 ° C, a sulfur content of 2 to 15 ppm by mass, The group content is 10-25% by volume and the total naphthene content is 20-60% by volume.
  • the "boiling point range” in the present specification is measured according to the method described in JIS-K-2254 "Distillation test method” or ASTM-D86.
  • the “sulfur content” in this specification is based on the total amount of light oil measured according to the method described in JIS-K-2541 “Sulfur content test method” or ASTM-D5453. The mass content of sulfur.
  • total aromatic content and “polycyclic aromatic content” described later in this specification are published by the Japan Petroleum Institute, JPI-5S- 49 -It is calculated from the volume percentage (volume%) of each aromatic content measured in accordance with the method described in 97 “Hydrocarbon type test method – High performance liquid chromatograph method”.
  • total naphthene content and “olefin content” described later in this specification are AS TM-D2786-91 TStandard Test Method for Hydrocarbon Types An alysis of Gas— Oil Saturates Fraction by High Ionizing Voltage Mass. It is measured according to the method described in Spectrometry].
  • the fraction lighter than the boiling point 150 ° C or heavier than the boiling point 380 ° C is less than 95% by volume
  • An increase in the light fraction may lead to an increase in LPG production, and an increase in the heavy fraction may cause the polycyclic aromatic hydrogenation reaction or conversion reaction to paraffin to not proceed sufficiently. It becomes easier to create new facilities. This is the same even when the raw oil is hydrorefined and used.
  • the sulfur content in the raw oil used in the present invention is 2 to 15 ppm by mass, preferably 3 to: L0 ppm by mass, and more preferably 4 to 9 ppm by mass.
  • S 15 mass ppm When the sulfur content in the feedstock exceeds S 15 mass ppm, the activity of the hydrotreating catalyst tends to decrease and the desulfurization reaction and aromatic hydrogenation reaction tend not to proceed sufficiently.
  • the sulfur content in the feedstock is less than 2 ppm by mass, the reaction temperature required to remove the sulfur content decreases, and aromatic water Elementary reaction and conversion reaction from naphthene to paraffin tend not to proceed sufficiently
  • the naphthene component that is a cyclic saturated hydrocarbon in addition to the aromatic component, the naphthene component that is a cyclic saturated hydrocarbon, the paraffin component that is an acyclic saturated hydrocarbon, and the olefin component that is an unsaturated hydrocarbon are generally included.
  • the total aromatic content in the feed oil used in the present invention is 10 to 25% by volume, preferably 11 to 21% by volume. If the total aromatic content of the feedstock exceeds 25% by volume, a long contact time, that is, an excessive reaction column volume is required to reduce the total aromatic content to 3% by volume or less in the first step. As a result, new capital investment is required and capital investment tends to be excessive.
  • the total aromatic content in the feedstock is less than 10% by volume, the operating conditions necessary for aromatic hydrogenation are more severe than the operating conditions required for desulfurization. The cost tends to increase and the economic advantage of the present invention tends to decrease.
  • the polycyclic aromatic component content is preferably 1 to 7% by volume based on the raw material oil. It is more preferable that the capacity is%. If the polycyclic aromatics content in the feedstock exceeds 7% by volume, capital investment tends to be excessive to achieve the specified polycyclic aromatics content in the product oil. If it is less than 1, it tends to be difficult to effectively obtain the effects of the present invention.
  • the total naphthene content in the feedstock according to the present invention is in the range of 20-60% by volume, more preferably 25-45% by volume. If the total naphthene content in the feedstock is less than 20% by volume, the feedstock will originally contain a high cetane number and a large amount of paraffin, and the degree of improvement in cetane number due to paraffin conversion of naphthene will be small. Therefore, the superiority of the present invention is reduced. On the other hand, when the total naphthene content in the feedstock exceeds 60% by volume, the total amount of aromatics and naphthenes in the feedstock tends to increase.
  • the olefin content in the feedstock is preferably 1 vol% or less.
  • polymerization in the reaction column is performed in the first step. Due to this reaction, the catalyst layer filled with the first hydrogenation catalyst tends to be clogged.
  • the feedstock oil may be a mixture of petroleum fractions distilled off as long as it is a hydrorefined petroleum hydrocarbon that satisfies the above-mentioned properties.
  • it may be obtained by desulfurization treatment in a hydrodesulfurization apparatus of straight-distilled oil having a predetermined boiling range that is distilled by the atmospheric distillation apparatus of raw oil.
  • a petroleum fraction having a predetermined boiling range obtained from a hydrocracking device, a residual oil direct desulfurization device, a fluid catalytic cracking device or the like is mixed with the above-mentioned straight-running oil, and then the mixed oil is hydrodesulfurized.
  • the petroleum fraction obtained in this way may be used as a feedstock.
  • a petroleum fraction having a predetermined boiling range obtained by hydrocracking a vacuum gas oil fraction obtained from a vacuum distillation apparatus in a hydrocracking apparatus may be used as one kind of raw material oil.
  • each hydrorefining device that uses a mixture of kerosene fractions and gas oil fractions from each device that have been individually hydrorefined and then brought to a specified boiling range can be used as the feedstock oil.
  • a mixture of the resulting product oil may be used.
  • the hydrodesulfurization conditions for obtaining the feedstock oil may be those used when processing using a hydrodesulfurization apparatus common in petroleum refining. That is, reaction temperature 250 ⁇ 380 ° C, hydrogen partial pressure 2 ⁇ 8MPa, liquid space velocity (LHSV) O. 3 ⁇ : LO. Hydrogen Z oil ratio 100 ⁇ 50 ONLZL, hydrodesulfurization treatment is preferred under the following conditions.
  • a catalyst provided in this hydrodesulfurization apparatus a general hydrodesulfurization catalyst in which an active metal is supported on a carrier can be used.
  • the active metal species sulfides of group 6A and group 8 metals (eg, Co—Mo, Ni—Mo, Ni—Co—Mo, Ni—W, etc.) may be used.
  • the carrier a porous inorganic oxide mainly composed of alumina may be used!
  • the hydrocracking conditions for obtaining the feedstock oil may be the conditions used when processing using a hydrocracking apparatus common in petroleum refining. That is, reaction temperature 300 ⁇ 450 ° C, hydrogen partial pressure 5 ⁇ 18MPa, liquid space velocity (LHSV) O. 1 ⁇ 8. Hydrogen Z oil ratio 300 ⁇ 20 OONLZL is preferable when hydrocracking treatment is performed under the following conditions.
  • a catalyst provided in this hydrocracking apparatus a general hydrocracking catalyst in which an active metal is supported on a carrier can be used.
  • the active metal species sulfides of group 6A and group 8 metals (eg, Co-Mo, Ni-Mo, Ni-Co-Mo, Ni-W, etc.) are usually used.
  • a substance containing a solid acid such as an inorganic complex acid zeolite or the like may be used.
  • the above-mentioned hydrodesulfurization catalyst and hydrocracking catalyst may be used in combination as a catalyst for obtaining raw material oil.
  • the reaction conditions and the types of catalysts used in hydrorefining to obtain feedstock are not particularly limited as long as the properties of the feedstock obtained satisfy the above conditions. Nah ...
  • each device or a combination of both devices is not particularly limited, but from the products obtained by these hydrorefining. It is desirable to remove hydrogen sulfide as much as possible using a gas-liquid separation tower or a predetermined hydrogen sulfide hydrogen removal facility. For example, in a general gas oil or kerosene desulfurization apparatus, it is preferable to separate hydrogen sulfide, which is a gas component, from a fraction from a reaction tower for hydrodesulfurization by a gas-liquid separation tower.
  • the amount of hydrogen sulfide contained therein will be extremely small, so that it is more suitable as the feedstock according to the present invention. Become. Even when hydrogen sulfide is mixed in the raw material oil, the object and effects of the present invention can be achieved by setting appropriate hydrotreating conditions in the production method of the present invention.
  • the feed oil is hydrotreated in the presence of the first hydrogenation catalyst to obtain a first product oil having a total aromatic content of 3% by volume or less.
  • the first hydrogenation catalyst used in the first step is preferably one in which at least one metal selected from the group consisting of group 8 metal power is supported as an active metal on a porous support.
  • the carrier for the first hydrogenation catalyst is preferably one containing at least one metal oxide selected from the group consisting of tita, zircoaure, polya and silica and alumina.
  • the above components can be combined, but from the viewpoint of the sulfur resistance of the catalyst, silica-alumina, titer-alumina, poly-alumina, zirconia-alumina, titania-zirconia Alumina, silica-boria Alumina
  • the composition ratio of alumina and other components in the carrier is not particularly limited, but the content of alumina is preferably 90% by mass or less, more preferably 60% by mass or less, more preferably 60% by mass or less based on the total amount of the carrier. Preferably it is 40 mass% or less.
  • the lower limit of the alumina content is not particularly limited, but is preferably 20% by mass or more based on the total amount of the carrier. If alumina exceeds 90% by mass, the sulfur resistance of the catalyst tends to be insufficient, and if it is less than 20% by mass, the moldability of the catalyst is lowered and its industrial production becomes difficult. It tends to be inclined.
  • the method for preparing the carrier is not particularly limited, and for example, it is prepared as follows. First, in order to obtain a carrier, an “alumina precursor” such as an alumina gel-containing liquid, boehmite powder, alumina suspension or kneaded product obtained by a conventional method is prepared. Next, in order to introduce metal oxides other than alumina, the acetate, chloride, nitrate, sulfate, naphthenate or various coordination compounds of the metal are dissolved in water or an organic solvent. The resulting mixture is added to the alumina precursor or blended by a method such as coprecipitation.
  • an “alumina precursor” such as an alumina gel-containing liquid, boehmite powder, alumina suspension or kneaded product obtained by a conventional method is prepared.
  • metal oxides other than alumina the acetate, chloride, nitrate, sulfate, naphthenate or various coordination compounds of the metal are dissolved in water or an organic solvent.
  • nitrates, acetates or salts are preferred, and nitrates and acetates are more preferred.
  • a carrier is obtained by kneading, drying, molding, firing and the like of this blend as necessary.
  • the metal oxide that modifies the support is obtained by calcining the support and then converting the metal acetate, chloride, nitrate, sulfate, naphthenate or various coordination compounds into water or an organic solvent.
  • the dissolved material may be introduced by impregnating the carrier.
  • the composite oxide or the like is prepared.
  • the support may be prepared by adding the above-mentioned metal oxide precursor alumina gel, other hydroxide gel or an appropriate solution, followed by kneading as described above.
  • metal oxide precursor alumina gel, other hydroxide gel or an appropriate solution followed by kneading as described above.
  • it can be molded into a shape such as a substantially cylindrical shape having a substantially circular cross section and a four-leaf pillar shape having a four-lobe cross section by extrusion molding.
  • reaction conditions of the first step in the present invention the reaction temperature one hundred seventy to three hundred and twenty ° C, a hydrogen partial pressure 2 to 10 MPa, liquid hourly space velocity (LHSV) O. l ⁇ 4h _1, hydrogen Z oil ratio 250 ⁇ 800NLZL Reaction temperature 180-305 ° C, hydrogen partial pressure 4-8MPa, liquid space velocity (LHS V) l. 0-3.
  • the hydrogen Z oil ratio is more preferably 300 to 700 NLZL.
  • a lower reaction temperature is advantageous for the hydrogenation reaction, but if the reaction temperature is less than 170 ° C, the desulfurization reaction tends not to proceed.
  • the reaction temperature exceeds 320 ° C, the life of the catalyst is shortened, and the formation of aromatics is advantageous in terms of chemical equilibrium, and the aromatic content of the first product oil tends to increase.
  • the higher the hydrogen partial pressure and the hydrogen Z oil ratio the more the desulfurization reaction and the hydrogenation reaction tend to be promoted.
  • the hydrogen partial pressure and the hydrogen Z oil ratio are less than the lower limit, desulfurization and aromatic hydrogenation reaction tend not to proceed.
  • the hydrogen partial pressure and hydrogen Z oil ratio exceed the above upper limits, excessive capital investment tends to be required.
  • the above reaction conditions are adjusted so that the total aromatic content in the obtained first product oil is 3% by volume or less, preferably 1% by volume or less. If the total aromatic content in the first product oil exceeds 3% by volume, the conversion reaction from naphthene to paraffin in the second step will not proceed easily, and light oil with excellent environmental characteristics and high cetane number will be produced. It tends to be difficult to obtain.
  • the olefin content in the first product oil is preferably 1% by volume or less.
  • the catalyst layer filled with the second hydrogenation catalyst tends to be clogged in the second step due to a reaction such as polymerization in the reaction tower.
  • the above-mentioned first product oil is hydrotreated in the presence of the second hydrogenation catalyst containing the crystalline molecular sieve component, and the above conditions (1) and (2) are satisfied.
  • the “crystalline molecular component” in the present specification means a molecular crystal and a solid crystal having a function.
  • the second hydrogenation catalyst used in the second step is not particularly limited as long as it contains a crystalline molecular sieve component.
  • the crystalline molecular sieve component include zeolite.
  • zeolite As the component constituting the crystallite skeleton of zeolite, a force including silica, alumina, titanium, polya, gallium and the like.
  • Zeolite containing silica and alumina, that is, aluminosilicate is preferable.
  • Examples of the crystal structure of zeolite include faujasite type, beta type, mordenite type, and pentasil type.
  • the crystalline molecular sieve component according to the present invention has an alumina content adjusted according to the stoichiometric ratio of the raw materials in order to stably obtain a desired crystal structure, or a predetermined hydrothermal treatment and Z Alternatively, an acid-treated one can be used.
  • the faujasite type zeolite is more preferable as the crystalline molecular sieve component, which is preferably a faujasite type or beta type zeolite.
  • Y type zeolite is used as the crystalline molecular sieve component according to the present invention, and is preferably super-stabilized Y type that is super-stabilized by hydrothermal treatment and Z or acid treatment.
  • USY Zeolite
  • This USY zeolite has a fine pore structure called a micropore of 20A or less, which Y-type zeolite originally has, and new pores in the range of 20-: LOO A. As a result, the conversion from naphthene to paraffin can be promoted more efficiently.
  • Known conditions can be adopted as hydrothermal treatment conditions for obtaining US Y zeolite.
  • the molar ratio of silica Z-alumina is preferably 10 to 120, more preferably 15 to 70. More preferably, it is 20-50.
  • silica / alumina ratio is higher than 120, the acid properties (acid point, acid strength, etc.) of zeolite are not good for the conversion of naphthene to paraffin, and the conversion activity from naphthene tends to decrease.
  • the silica Z alumina ratio is lower than 10, the acidity becomes strong and the coke formation reaction is promoted, so that the activity of the second hydrogenation catalyst tends to be rapidly reduced.
  • the crystalline molecular sieve component according to the present invention it is preferable to use the one formed by the tableting method after synthesis as it is, but the one formed by mixing with the binder component.
  • the binder component is silica alumina, tita-alumina, boria-alumina, zirconia-alumina, titania-zirconia-alumina that is used in the first step as described above.
  • Silica Boria-Alumina, Silica-Zirconia-Alumina, Silica-Titania Alumina, Silica-Titanium Zircona-Alumina may be any of them.
  • the zeolite content in the second hydrogenation catalyst is preferably 10% by mass or more, more preferably 30% by mass or more, and even more preferably 50% by mass or more.
  • the shape of the molded catalyst is not particularly limited, but any shape such as a cylinder, macaroni type or spherical shape obtained by extrusion molding can be selected.
  • a portion having a hydrogenation catalyst power not containing a crystalline molecular sieve component is provided after a portion having a hydrogenation catalyst power containing a crystalline molecular sieve component. It may be provided. In the latter part, the same catalyst as in the first step can be used. As a result, among the products obtained by the naphthene conversion reaction, radical products and compounds that are susceptible to acid-acid reactions due to unstable structure are stabilized by hydrogenation reaction, etc. Generation of sludge (solid matter) and coloration due to oxidative condensation polymerization can be prevented.
  • the ratio of the second hydrogenation catalyst to the total amount of the first hydrogenation catalyst and the second hydrogenation catalyst is not particularly limited, but the ratio of the hydrogenation catalyst containing the crystalline molecular sieve component is the first hydrogenation catalyst.
  • the second hydrogenation catalyst (a hydrogenation catalyst containing a crystalline molecular sieve component and a hydrogenation catalyst not containing a crystalline molecular sieve component) is preferably 30% by volume or more. More preferably 40% by volume or more. When the proportion of the hydrogenation catalyst containing the crystalline molecular sieve component is below 30% by volume, the naphthene conversion activity tends to be low.
  • reaction conditions of the second step in the present invention the reaction temperatures 200 to 280 ° C, a hydrogen partial pressure 2 to 10 MPa, liquid hourly space velocity (LHSV) O. l ⁇ 2h _1, hydrogen Z oil ratio 250 ⁇ 800NLZL
  • reaction temperature 220 to 270 ° C
  • hydrogen partial pressure 4 to 8 MPa
  • liquid space velocity LHS V
  • a lower reaction temperature is advantageous for the hydrogenation reaction, but when the reaction temperature is lower than 200 ° C, the activity of the naphthene conversion reaction tends to decrease. On the other hand, the higher the reaction temperature, the more advantageous for the naphthene conversion reaction.
  • the reaction temperature exceeds 280 ° C, the yield of the product with a boiling point of less than 150 ° C increases, and the target gas oil fraction is collected. The rate tends to decrease.
  • the hydrogen partial pressure and hydrogen Z oil ratio are generally higher, both the hydrogenation reaction and the naphthene conversion reaction tend to be promoted. When the hydrogen partial pressure and the hydrogen Z oil ratio are less than the above lower limits, the hydrogenation reaction and the naphthene conversion reaction tend not to proceed.
  • the reaction conditions are adjusted so that the content of the light petroleum fraction having a boiling point range of less than 150 ° C is 16 vol% or less in the second product oil obtained. More preferably, the reaction conditions are adjusted so that the content of the light petroleum fraction is 12% by volume or less, more preferably 8% by volume or less. If the light petroleum fraction exceeds 16% by volume, the yield of light oil obtained from the second product oil decreases, making it difficult to produce light oil with sufficient efficiency.
  • the sum of the total aromatic content and the total naphthene content is the sum of the total aromatic content and the total naphthene content in the raw material oil.
  • the reaction conditions are adjusted so as to be 80% or less, preferably 70%. Excellent environmental characteristics when the total aromatic content and total naphthene content exceed 80% of the total aromatic content and total naphthene content in the above feedstock. It tends to be difficult to obtain light oil having a high cetane number.
  • the total aromatic content in the second product oil is 3% by volume or less, more preferably 1% by volume or less. If the total aromatic content exceeds 3% by volume, diesel exhaust Since the effect of reducing particulates is reduced, it becomes difficult to obtain light oil having excellent environmental characteristics and a high cetane number, and the object effect of the present invention is not achieved.
  • the polycyclic aromatic content in the second product oil is preferably 0.2% by volume or less, and more preferably 0.1% by volume or less. When the polycyclic aromatic content exceeds 0.2% by volume, the particulates in the diesel exhaust gas tend to increase.
  • the total of the polycyclic aromatic content and the polycyclic naphthene content in the second product oil is preferably 13% by volume or less, more preferably 10% by volume or less.
  • the cetane number is difficult to improve, and good fuel characteristics tend to be difficult to obtain.
  • the active metal supported in the first hydrogenation catalyst and the second hydrogenation catalyst according to the present invention can be used for desulfurization activity, aromatic hydrogenation activity, and naphthenic paraffin to achieve the object effects of the present invention.
  • a plurality of metals may be selected and combined as the active metal of the hydrogenation catalyst.
  • Pt—Pd, Pt—Rh, Pt—Ir, Rh—Ir, Rh—Pd, Ir—Pd, Pt —Pd—Ir, Pt—Rh—Ir, Pt—Rh—Pd, Rh—Ir—Pd, etc. may be employed.
  • Pt—Pd, Pt—Rh, Pt—Ir, and Pt—Pd from the viewpoints of desulfurization activity, aromatic hydrogenation activity, naphthene conversion activity to paraffin, etc. that can achieve the object effects of the present invention.
  • —Ir, Pt—Rh—Ir or Pt—Rh—Pd is more preferred Pt—Pd
  • Pt—Ir or Pt—Pd—Ir is more preferred Pt—Pd is particularly preferred.
  • the amount of these active metals supported is not particularly limited, but the amount of the metal is relative to the total amount of the catalyst from the viewpoints of desulfurization activity, aromatic hydrogenation activity, naphthene conversion activity to paraffin, etc. that can achieve the object effects of the present invention.
  • LO mass% is preferred 0.1 to 5 mass% is more preferred 0.1 to 3 mass% is more preferred.
  • an inorganic salt or complex salt compound of the active metal that is, an aqueous solution or water solution of carbonate, nitrate, sulfate, organic acid salt or oxide, etc. If a method using an organic solvent or a water-insoluble organic solvent is used, an impregnation method or an ion-exchange method or the like, which is used in a conventional hydrogenation catalyst, may be employed. If multiple metals are supported, they can be supported simultaneously using a mixed solution or sequentially using a single solution!
  • the active metal may be supported on the support after completion of the entire preparation process of the support, or the active metal is supported on an appropriate oxide, composite oxide, crystalline molecular sieve, or the like in the intermediate process of the support preparation. Thereafter, steps such as a gel matching step, heat compression, and kneading may be performed, but it is preferable to perform the steps after the completion of the entire carrier preparation step.
  • the hydrogenation catalyst according to the present invention can be obtained by firing an impregnated and supported active metal under desired conditions.
  • the first hydrogenation catalyst and the second hydrogenation catalyst according to the present invention are preferably used after pre-reduction treatment in a hydrogen stream.
  • This preliminary reduction treatment is usually performed by circulating a gas containing hydrogen through a reaction tube (reaction tower) filled with a hydrogenation catalyst and applying heat of 200 ° C. or higher to the hydrogenation catalyst according to a predetermined procedure. .
  • the active metal supported by the catalyst is reduced, and hydrogenation activity and naphthene conversion activity can be expressed more effectively.
  • the apparatus for hydrotreating the feedstock oil in this way may be of any configuration, and the reaction towers packed with the catalyst may be used singly or in combination.
  • a gas-liquid separation facility or other sulfide is provided between the reaction towers.
  • a hydrogen removal facility may be provided, or a facility for additionally injecting hydrogen may be provided.
  • the reaction mode of the hydrotreating apparatus used in the present invention may be a fixed bed system. That is, hydrogen can take either a countercurrent or a cocurrent flow with respect to the feedstock, or it can have a plurality of reaction towers and a combination of countercurrent and cocurrent flow. A common format is downflow, and there is a gas-liquid co-current format.
  • the reaction tower may be composed of a plurality of catalyst beds. Between each catalyst bed, hydrogen gas may be injected for the purpose of removing reaction heat or increasing the hydrogen partial pressure (Taenti hydrogen).
  • the hydrorefined gas oil obtained by the preferred embodiment of the present invention described above has a sulfur content of 1 mass ppm or less and a total aromatic content of 3 vol% or less.
  • Ma the present inventors have experimented with the fact that this hydrorefined diesel oil can greatly improve the cetane number with respect to the feedstock oil. Confirmed by This is thought to be due to the conversion to a higher cetane number and higher hydrocarbon content by hydrogenation of aromatics and conversion to naphthenic paraffins. This cetane number is an indicator of flammability. The higher the value, the better the ignitability, and the improvement of combustion efficiency can be expected for diesel engines.
  • the cetane number in this specification is a cetane number measured according to the method described in JIS-K2280 "Testing method for octane number and cetane number and cetane index calculation method".
  • the cetane number of petroleum fractions is simply calculated by the cetane index calculated by the cetane index calculation method described in the above 6JIS-K2280 “Octane number and cetane number test method and cetane index calculation method”. , The increase or decrease can be confirmed.
  • the light oil obtained by a preferred embodiment of the present invention may be used alone as diesel light oil!
  • a light oil composition mixed with other base materials may be used as diesel light oil.
  • Other base materials include synthetic light oil or synthetic kerosene obtained by using a so-called synthesis gas composed of hydrogen and carbon monoxide as a raw material and via a Fischer-Tropsch reaction or the like. These synthetic kerosene and synthetic light oil contain little aromatics and are mainly saturated hydrocarbons, so they usually have a high cetane number.
  • a well-known method can be used as a manufacturing method of synthesis gas, and it is not specifically limited.
  • the blending ratio of the synthetic light oil in the light oil composition is preferably 30% by volume or less, more preferably 20% by volume or less, and still more preferably 10% by volume or less.
  • the blending ratio of the synthetic kerosene in the light oil composition is preferably 60% by volume or less, more preferably 50% by volume or less, and still more preferably 40% by volume or less.
  • aqueous sodium silicate solution (concentration 29% by mass, 2350 g) was gelled under pH 4 conditions and then aged at 60 ° C. and pH 7 for 2 hours to obtain a slurry.
  • an aqueous solution containing zirconium sulfate (tetrahydrate, 350 g) was added to the resulting slurry, and the slurry after addition was further adjusted to PH7 to produce silica-zircoua complex hydroxide.
  • This carrier is impregnated with an active metal by a conventional method using a mixed aqueous solution of tetraammineplatinum (II) chloride and tetraamminepalladium (II) chloride, the concentration of which is adjusted to match the water absorption rate of the carrier. I was damned. Then, it was dried in the atmosphere at 110 ° C. for 1 hour and calcined at 300 ° C. for 2 hours to obtain a first hydrogenation catalyst. The supported amounts of platinum and palladium in the first hydrogenation catalyst were 0.3% by mass and 0.5% by mass, respectively, based on the entire catalyst.
  • the obtained ammonia-type zeolite was added to a mixed solution of tetraammineplatinum ( ⁇ ) chloride and tetraamminepalladium ( ⁇ ) chloride, the concentration of which was adjusted so as to match the water absorption rate of the carrier, The mixture was stirred at 70 ° C, and the active metal was supported by the ion exchange method. Zeolite carrying active metal was collected by filtration, dried in air at 110 ° C for 1 hour, and calcined at 300 ° C for 2 hours. The obtained zeolite was kneaded with a commercially available alumina gel (manufactured by Condea) and molded to obtain a second hydrogenation catalyst. The supported amounts of platinum and palladium in the second hydrogenation catalyst are 0.3% by mass and 0.5% by mass, respectively, with respect to the total catalyst. Met. The ratio of zeolite and alumina was 70:30 by mass ratio.
  • the first reaction tube (inner diameter 20mm) filled with the first hydrogenation catalyst (20mL) and the second reaction tube (inner diameter 20mm) filled with the second hydrogenation catalyst (20mL) are connected in series in a fixed bed flow reactor ( After being attached to the down flow, reduction pretreatment was performed as pretreatment under conditions of hydrogen partial pressure 5 MPa, 300 ° C, 5 hours. Thereafter, the feedstock oil having properties shown in Table 2 was passed through the reactor under the conditions shown in Table 1, and a hydrorefining test was conducted.
  • the feedstock oil is obtained by hydrorefining a gas oil equivalent fraction obtained by atmospheric distillation of Middle Eastern crude oil.
  • IBP 3 ⁇ 4 JIS-K-2254 is the initial stop point defined in “EP” 3 ⁇ 4 JIS-K-2254 and is the end point.
  • total aromatic content + total naphthene content) yield is the total aromatic content and total naphthene content in the second product oil relative to the total amount of total aromatic content and total naphthene content in the feedstock oil. It is a percentage of the total amount.
  • the “light oil yield” is the yield of a fraction having a boiling point range of 150 to 380 ° C.
  • Light fraction yield refers to the yield of lighter V and fractions than diesel oil, that is, fractions with a boiling range of less than 150 ° C.
  • the starting power of the hydrorefining test was 10 days, and the total aromatic content of the product oil (first product oil) distilled from the first reaction tube filled with the first hydrogenation catalyst was 0.8.
  • the olefin content was 0.1% by volume, and the sulfur content was 0.6 mass ppm.
  • Table 2 shows the properties of the second product oil on the 10th day from the start of the hydrorefining test.
  • Hydrogen gas was charged in the same manner as in Example 1 except that the amount of the first hydrogenation catalyst charged into the first reaction tube was changed to 20 mL force 8 mL, and the liquid space velocity in the first step was changed from 2.0 h _1 to 5.0 h _1.
  • a chemical purification test was conducted.
  • the total oil content of the product oil (first product oil) that distills from the first reaction tube charged with the first hydrogenation catalyst is 6.8 vol%, and the olefin content is 0.2 vol. %, And the sulfur content was 2.6 mass ppm.
  • Table 2 shows the properties of the second product oil on the 10th day from the start of the hydrorefining test.
  • a hydrorefining test was carried out in the same manner as in Example 1 except that the catalyst charged in the second reaction tube (inner diameter 20 mm) was changed from the second hydrogenation catalyst (20 mL) to the first hydrogenation catalyst (20 mL).
  • the total oil content of the product oil (first product oil) distilling from the first reaction tube charged with the first hydrogenation catalyst is 0.8 vol%, and the olefin content is 0.1 vol. %, And the sulfur content was 0.6 mass ppm.
  • Second generation on the 10th day from the start of the hydrorefining test Table 2 shows the properties of the synthesized oil.
  • both the environmental characteristics and the combustion characteristics are such that the sulfur content is 1 mass ppm or less, the total aromatic content is 3 vol% or less, and the strength is also high cetane number. It is possible to provide a method for producing hydrorefined gas oil that can efficiently and reliably produce light oil with excellent operating performance without special operating conditions and capital investment.

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  • Engineering & Computer Science (AREA)
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Abstract

La présente invention concerne un procédé de fabrication de gazole hydroraffiné, comprenant la phase d’hydrogénation d’une huile d’hydroraffinage contenant au moins 95% en volume d’une fraction de distillation d’une fourchette de points d’ébullition de 150 à 380ºC et ayant une teneur en soufre de 2 à 15 ppm en masse, une teneur aromatique totale de 10 à 25% en volume, et une teneur totale en naphtène de 20 à 60% en volume en présence d’un catalyseur d’hydrogénation pour élaborer une huile générée d’une teneur aromatique totale ne dépassant pas 3% en volume, et la phase d’hydrogénation de l’huile générée ci-dessus en présence d’un catalyseur d’hydrogénation comprenant une composante de tamis moléculaire cristallin pour élaborer une huile générée ne contenant pas plus de 16% en volume d’une fraction de distillation de pétrole d’une fourchette de points d’ébullition inférieure à 150ºC et satisfaisant à l’exigence selon laquelle le total de la teneur aromatique totale et de la teneur totale en naphtène ne dépasse pas 80% du total de la teneur aromatique totale et de la teneur totale en naphtène dans l’huile d’hydroraffinage.
PCT/JP2005/018127 2004-10-01 2005-09-30 Procédé de fabrication de gazole hydroraffiné, gazole hydroraffiné et composition de gazole WO2006038555A1 (fr)

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EP05788266A EP1818385A4 (fr) 2004-10-01 2005-09-30 Procédé de fabrication de gazole hydroraffiné, gazole hydroraffiné et composition de gazole
US11/664,260 US20080308459A1 (en) 2004-10-01 2005-09-30 Process for Producing Hydrorefined Gas Oil, Hydrorefined Gas Oil, and Gas Oil Composition

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JP2010215723A (ja) * 2009-03-13 2010-09-30 Idemitsu Kosan Co Ltd 軽油基材の製造方法
JP5379062B2 (ja) * 2010-03-31 2013-12-25 Ｊｘ日鉱日石エネルギー株式会社 軽油基材又は軽油組成物の製造方法
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JP2006104271A (ja) 2006-04-20

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