AU2007226057A1 - Process for production of hydrocarbon oil and hydrocarbon oil - Google Patents

Process for production of hydrocarbon oil and hydrocarbon oil Download PDF

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AU2007226057A1
AU2007226057A1 AU2007226057A AU2007226057A AU2007226057A1 AU 2007226057 A1 AU2007226057 A1 AU 2007226057A1 AU 2007226057 A AU2007226057 A AU 2007226057A AU 2007226057 A AU2007226057 A AU 2007226057A AU 2007226057 A1 AU2007226057 A1 AU 2007226057A1
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fraction
hydrocarbon oil
mass
boiling point
content
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AU2007226057A
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AU2007226057B2 (en
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Yoshifumi Chiba
Shinya Takahashi
Yuichi Tanaka
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Eneos Corp
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Nippon Oil Corp
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    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G65/00Treatment of hydrocarbon oils by two or more hydrotreatment processes only
    • C10G65/14Treatment of hydrocarbon oils by two or more hydrotreatment processes only plural parallel stages only
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G45/00Refining of hydrocarbon oils using hydrogen or hydrogen-generating compounds
    • C10G45/02Refining 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
    • C10G45/04Refining 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 characterised by the catalyst used
    • C10G45/12Refining 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 characterised by the catalyst used containing crystalline alumino-silicates, e.g. molecular sieves
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G47/00Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
    • C10G47/02Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
    • C10G47/10Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used with catalysts deposited on a carrier
    • C10G47/12Inorganic carriers
    • C10G47/16Crystalline alumino-silicate carriers
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/10Feedstock materials
    • C10G2300/1022Fischer-Tropsch products
    • CCHEMISTRY; METALLURGY
    • C10PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10GCRACKING 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
    • C10G2300/00Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/20Characteristics of the feedstock or the products
    • C10G2300/30Physical properties of feedstocks or products
    • C10G2300/301Boiling range

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

Description

CERTIFICATE OF VERIFICATION I, Shiro TERASAKI Japanese Patent Attorney Registered No. 9265 of SOEI PATENT & LAW FIRM Ginza First Bldg., 10-6, Ginza 1-chome, Chuo-ku, Tokyo 104-0061 Japan states that the attached document is a true and complete translation to the best of my knowledge of International Patent Application No. PCT/JP2007/052618 Dated this 14th day of August, 2008 Signature of translator: S ro ERASAU-verification(PCT) AU-verification(PCT) FPO6-0521-00 DESCRIPTION PROCESS FOR PRODUCTION OF HYDROCARBON OIL AND HYDROCARBON OIL TECHNICAL FIELD 5 [0001] The present invention relates to a hydrocarbon oil and a method of manufacturing the same, and more specifically to a hydrocarbon oil useful as a diesel fuel base stock and a method of manufacturing the same. BACKGROUND ART 10 [0002] In recent years, from the viewpoint of reducing the burden on the environment, there have been calls for environmentally-friendly clean liquid fuels having low sulfur and aromatic hydrocarbon contents. In the petroleum industry, studies have thus been carried out into Fischer-Tropsch synthesis (hereinafter abbreviated to "FT synthesis") 15 using carbon monoxide and hydrogen as starting materials as a method of manufacturing a clean fuel. According to FT synthesis, a liquid fuel base having a high paraffin content and not containing sulfur can be manufactured, and hence there are great expectations. [0003] However, a synthetic oil obtained through FT synthesis 20 (hereinafter sometimes referred to as an "FT synthetic oil") has a high normal paraffin content, and contains oxygen-containing compounds such as alcohols, and hence it is difficult to use the synthetic oil as a fuel as is. More specifically, such a synthetic oil has an insufficient octane rating for use as automobile gasoline, and moreover has an insufficient 25 low-temperature fluidity for use as diesel fuel. Moreover, oxygen containing compounds such as alcohols have an adverse effect on the 1 FPO6-0521-00 oxidation stability of a fuel. In general, an FT synthetic oil is thus used as a fuel base after having been hydrotreated so as to convert normal paraffin in the synthetic oil into isoparaffin and convert oxygen containing compounds into other substances. 5 [0004] For example, in the case of manufacturing a diesel fuel base stock, a kerosene base stock, an aviation fuel base or the like, the low temperature fluidity of the fuel base is improved by mixing together as appropriate a middle fraction having a high isoparaffmn content obtained by hydrocracking a heavy wax component of the FT synthetic oil, and a 10 middle fraction having an increased paraffin isomerization degree obtained by hydroisomerizing a middle fraction of the FT synthetic oil, or the like (for example, see Patent document 1 and 2.). [0005] Patent document 1: International Patent Application Laid-open No. 00/020535. 15 Patent document 2: French Patent Application Laid-open No. 2826971. DISCLOSURE OF THE INVENTION PROBLEMS TO BE SOLVED BY THE INVENTION [0006] From the viewpoint of preventing fuel pump problems or heat chamber seizure due to oil film disruption, fuel used in diesel 20 automobiles preferably exhibits a certain kinematic viscosity at normal temperature and high temperature. For example, in the no. 2 light oil kinematic viscosity standard of JIS (Japanese Industrial Standards) K2283, the kinematic viscosity at 30 oC is stipulated as being not less than 2.5 mm 2 /s. A hydrocarbon oil to be used as a diesel fuel base 25 stock from out of a middle fraction obtained from an FT synthetic oil must thus have both the low-temperature fluidity and the kinematic 2 FPO6-0521-00 viscosity thereof sufficiently improved. [0007] Meanwhile, from hitherto there have been increasingly strong demands to reduce the cost of diesel fuel manufacture, and there is no exception to this for fuel manufacture using FT synthesis; it has thus 5 also become necessary to manufacture a hydrocarbon oil suitable as a diesel fuel base stock from an FT synthetic oil efficiently. [0008] However, the prior art such as above-mentioned Patent document 1 and Patent document 2 is mainly concerned with improving the low-temperature fluidity of a fuel base as described above; no art 10 has as yet been provided that is effective for obtaining a high yield of a hydrocarbon oil that has both good low-temperature fluidity and good kinematic viscosity at 30 oC. [0009] When obtaining a hydrocarbon oil, one could envisage, for example, a method of improving both the low-temperature fluidity and 15 the kinematic viscosity at 30 oC by narrowing the boiling point range for the fractionation; however, with this method, the amount of a diesel fuel base stock that can be manufactured from an FT synthetic oil is reduced, and hence the fuel manufacturing process becomes uneconomical. Moreover, if only a middle fraction obtained by 20 hydrocracking a heavy wax component of an FT synthetic oil is used as a diesel fuel base stock, then it may be possible to obtain both good low-temperature fluidity and good kinematic viscosity at 30 oC; however, the amount of the diesel fuel base stock that can be manufactured from the FT synthetic oil is limited, and hence it is 25 difficult to manufacture a sufficient amount of the fuel base. [0010] The present invention has been devised in view of the above 3 FPO6-0521-00 state of affairs; it is an object of the present invention to provide a hydrocarbon oil manufacturing method that enables a hydrocarbon oil having sufficiently good low-temperature fluidity and a kinematic viscosity at 30 oC of not less than 2.5 nmm 2 /s to be obtained with high 5 yield from an FT synthetic oil, and a hydrocarbon oil obtained using the method. MEANS FOR SOLVING THE PROBLEMS [0011] The present inventors carried out assiduous studies to attain the above object, and as a result accomplished the present invention upon 10 discovering that a hydrocarbon oil obtained by obtaining from an FT synthetic oil a middle fraction containing a specified amount of a fraction having a specified boiling point range and a wax component that is heavier than the middle fraction, separately hydrotreating each of the middle fraction and the wax component and then mixing the two 15 together, and fractionating the mixture to obtain a hydrocarbon oil containing a specified amount of a fraction having a specified boiling point, exhibits a pour point of not more than -7.5 oC and a kinematic viscosity at 30 oC of not less than 2.5 mm2/s, and moreover exhibits a sufficient yield relative to the starting material FT synthetic oil. 20 [0012] That is, a hydrocarbon oil manufacturing method of the present invention comprises fractionating a synthetic oil obtained through Fischer-Tropsch synthesis, so as to obtain a middle fraction having a content of a fraction of boiling point 150 to 360 oC of not less than 90 mass% and a content of a fraction of boiling point not less than 350 oC 25 of not more than 5 mass%, and a wax component that is heavier than the middle fraction, and bringing each of the middle fraction and the wax 4 FPO6-0521-00 component into contact with a hydrotreating catalyst in the presence of hydrogen, and then mixing together, and fractionating, so as to obtain a hydrocarbon oil having a content of a fraction of boiling point 150 to 360 oC of not less than 86 mass% and a content of a fraction of boiling 5 point not less than 350 oC of not less than 5 mass%. [0013] According to the hydrocarbon oil manufacturing method of the present invention, a hydrocarbon oil having sufficiently good low temperature fluidity and a kinematic viscosity at 30 'C of not less than 2.5 mm 2 /s can be obtained with high yield from an FT synthetic oil. 10 As a result, an environmentally-friendly diesel fuel can be manufactured economically. [0014] In the hydrocarbon oil manufacturing method of the present invention, preferably, the middle fraction is hydrotreated such that the content of hydrocarbons of boiling point not more than 150 oC in the 15 middle fraction is 3 to 9 mass% greater after the contact than before the contact with the hydrotreating catalyst. [0015] As a result, the pour point of the hydrocarbon oil can be further reduced while still securing a sufficient yield for the hydrocarbon oil. [0016] In the hydrocarbon oil manufacturing method of the present 20 invention, preferably, the wax component is hydrotreated such that the content of a fraction of boiling point not more than 360 oC in the wax component after the contact with the hydrotreating catalyst is 45 to 85 mass%. If this content is less than 45 mass%, then the yield for the hydrocarbon oil obtained will tend to decrease, and the low-temperature 25 fluidity of the hydrocarbon oil will tend to decrease. On the other hand, if this content is greater than 85 mass%, then the yield for the 5 FPO6-0521-00 hydrocarbon oil obtained will tend to decrease. [0017] In the hydrocarbon oil manufacturing method of the present invention, preferably, each of the hydrotreating catalyst brought into contact with the middle fraction and the hydrotreating catalyst brought 5 into contact with the wax component comprises a carrier containing 0.1 to 80.0 mass% of a crystalline zeolite and 0.1 to 60.0 mass% of a heat resistant amorphous metal oxide, and at least one metal selected from the group consisting of metals belonging to group VIII of the periodic table supported on the carrier. 10 [0018] In the hydrocarbon oil manufacturing method of the present invention, preferably, the middle fraction is brought into contact with the hydrotreating catalyst at a reaction temperature of 200 to 370 oC, a hydrogen partial pressure of 1.0 to 5.0 MPa, and a liquid hourly space velocity of 0.3 to 3.5 h-1, and the wax component is brought into 15 contact with the hydrotreating catalyst at a reaction temperature of 200 to 370 oC, a hydrogen partial pressure of 1.0 to 5.0 MPa, and a liquid hourly space velocity of 0.3 to 3.5 h- 1. [0019] Moreover, a hydrocarbon oil of the present invention is obtained through the hydrocarbon oil manufacturing method of the present 20 invention as described above, and has a pour point of not more than 7.5 oC, and a kinematic viscosity at 30 oC of not less than 2.5 mm 2 /s. Such a hydrocarbon oil has excellent quality as a diesel fuel base stock, and moreover can be obtained with high yield from an FT synthetic oil. According to the hydrocarbon oil of the present invention, an 25 environmentally-friendly diesel fuel can thus be realized at low cost. EFFECT OF THE INVENTION 6 FPO6-0521-00 [0020] According to the present invention, there can be provided a hydrocarbon oil manufacturing method that enables a hydrocarbon oil having sufficiently good low-temperature fluidity and a kinematic viscosity at 30 'C of not less than 2.5 mm 2 /s to be obtained with high 5 yield from an FT synthetic oil, and a hydrocarbon oil obtained using the method. BRIEF DESCRIPTION OF THE DRAWINGS [0021] FIG 1 is a flow diagram showing an example of a hydrocarbon oil manufacturing apparatus for implementing a hydrocarbon oil 10 manufacturing method of the present invention. Explanation of Reference Numerals [0022] 1: FT synthetic oil introduction flow path; 2, 4, 6: flow path; 3: middle fraction flow path; 5: wax component flow path; 7, 8: recovery flow path; 9: circulating flow path; 10: first distillation column; 20, 30: 15 hydrotreating apparatus; 22, 32: gas-liquid separation tank; 40: second distillation column, 100: hydrocarbon oil manufacturing apparatus BEST MODE FOR CARRYING OUT THE INVENTION [0023] Following is a detailed description of a preferred embodiment of the present invention with reference to the attached drawings. Note 20 that in the description of the drawings, same or equivalent elements are designated by the same reference numeral, and repeated description is omitted. [0024] FIG 1 is a flow diagram showing an example of a hydrocarbon oil manufacturing apparatus for implementing a hydrocarbon oil 25 manufacturing method of the present invention. The hydrocarbon oil manufacturing apparatus 100 shown in FIG 1 comprises an FT 7 FPO6-0521-00 synthetic oil introduction flow path 1 through which a starting material FT synthetic oil is introduced, a first distillation column 10 that fractionates the synthetic oil introduced in from the FT synthetic oil introduction flow path 1 into a light fraction, a middle fraction, and a 5 heavy wax component, a hydrotreating apparatus 20 that hydrogenates the middle fraction which is supplied in from the distillation column 10 via a middle fraction flow path 3, a hydrotreating apparatus 30 that hydrogenates the heavy wax component which is supplied in from the distillation column 10 via a wax component flow path 5, a gas-liquid 10 separation tank 22 for removing a gaseous component from the middle fraction that has passed through the hydrotreating apparatus 20, a gas liquid separation tank 32 for removing a gaseous component from the heavy wax component that has passed through the hydrotreating apparatus 30, and a second distillation column 40 that fractionates a 15 liquid component from the gas-liquid separation tank 22 and a liquid component from the gas-liquid separation tank 32. The gas-liquid separation tank 22 and the second distillation column 40, and the gas liquid separation tank 32 and the second distillation column 40 are connected together by a flow path 4 and a flow path 6 respectively. 20 [0025] Moreover, the first distillation column 10 has connected thereto a flow path 2 through which light wax is discharged out of the system. Furthermore, the second distillation column 40 has connected thereto a recovery flow path 8 for discharging the hydrocarbon oil of the present invention obtained through the fractionation, a recovery flow path 7 for 25 discharging a fraction lighter than the hydrocarbon oil, and a circulating flow path 9 for supplying a wax component heavier than the 8 FPO6-0521-00 hydrocarbon oil into the hydrotreating apparatus 30 for hydrotreating as required. [0026] Following is a detailed description of the hydrocarbon oil manufacturing method of the present invention with reference to the 5 hydrocarbon oil manufacturing apparatus 100 shown in FIG 1. [0027] (Fractionation of FT synthetic oil) First, there are no particular limitations on the FT synthetic oil used in the hydrocarbon oil manufacturing method of the present invention so long as the FT synthetic oil is produced through FT synthesis, although 10 the FT synthetic oil preferably contains not less than 80 mass% of hydrocarbons having a boiling point of not less than 150 oC based on the total amount of the FT synthetic oil, and not less than 35 mass% of hydrocarbons having a boiling point of not less than 360 oC based on the total amount of the FT synthetic oil. Here, the total amount of the 15 FT synthetic oil means the total amount of hydrocarbons having not less than 5 carbon atoms produced through the FT synthesis. [0028] For the first distillation column 10, two cut points are set when fractionating the FT synthetic oil, whereby a fraction having a boiling point of not more than the first cut point can be obtained as a light 20 fraction, a fraction having a boiling point between the first cut point and the second cut point as a middle fraction, and a fraction having a boiling point of not less than the second cut point as a bottom oil (heavy wax component). In the present embodiment, by setting the first cut point and the second cut point as appropriate, a middle fraction having a 25 content of a fraction of boiling point 150 to 360 oC of not less than 90 mass% and a content of a fraction of boiling point not less than 350 oC 9 FP06-0521-00 of not more than 5 mass%, and a wax component that is heavier than the middle fraction are obtained. [0029] The content of the fraction of boiling point 150 to 360 oC and the content of the fraction of boiling point not less than 350 oC (mass%) 5 in the middle fraction can be determined through analysis using a publicly known method, for example gas chromatography on a sample from the middle fraction flow path 3. [0030] Furthermore, in the present embodiment, in the first distillation column 10, the fractionation is preferably carried out such that the 10 fraction of boiling point not less than 350 oC is substantially not contained in the middle fraction. Moreover, the fractionation is preferably carried out such that not less than 15 mass% of a fraction of boiling point 300 to 350 oC is contained in the middle fraction. [0031] The first cut point and the second cut point are preferably set in 15 a range of 135 to 170 oC and in a range of 330 to 355 oC respectively, more preferably in a range of 145 to 155 oC and in a range of 345 to 355 oC respectively. [0032] Note that the number of cut points for the first distillation column 10 is not limited to being two, but rather three or more may be 20 set so long as the middle fraction and the wax component can be obtained as described above. [0033] (Hydrotreating of middle fraction) In the hydrotreating apparatus 20, the middle fraction obtained from the first distillation column 10 is hydrotreated. As the hydrotreating 25 apparatus 20, a publicly known fixed bed reaction column can be used. In the present embodiment, in the reaction column, a predetermined 10 FPO6-0521-00 hydrorefining catalyst is preferably packed into the fixed bed flow reactor, so that the middle fraction obtained from the first distillation column 10 is hydrorefined. Here, "hydrorefmiing" includes both hydrocracking and hydroisomerization. Furthermore, "cracking" 5 means chemical reaction accompanied by a reduction in molecular weight, and "isomerization" means conversion into a compound having a different carbon backbone while maintaining the molecular weight and the number of carbons in the molecule as is. [0034] An example of the hydrorefining catalyst is one in which a metal 10 belonging to group VIII of the periodic table is supported as an active metal on a carrier containing a solid acid. [0035] A suitable carrier is one containing at least one solid acid selected from crystalline zeolites such as ultrastable Y (USY) zeolites, HY zeolites, mordenite and 13 zeolites, and heat-resistant amorphous 15 metal oxides such as silica-alumina, silica-zirconia and alumina-boria. Furthermore, the carrier is more preferably one containing a USY zeolite, and at least one solid acid selected from silica-alumina, alumina-boria and silica-zirconia, yet more preferably one containing a USY zeolite and silica-alumina. 20 [0036] Such a USY zeolite is a Y zeolite that has been ultrastabilized through hydrothermal treatment and/or acid treatment, whereby in addition to a microporous structure of micropores of size not more than 20 A originally possessed by the Y zeolite, new pores of size in a range of 20 to 100 A are also formed. In the case of using a USY zeolite in 25 the carrier of the hydrorefining catalyst, there are no particular limitations on the mean particle diameter thereof, but this mean particle 11 FPO6-0521-00 diameter is preferably not more than 1.0 pm, more preferably not more than 0.5 pm. Moreover, for the USY zeolite, the silica/alumina molar ratio (the molar ratio of silica to alumina, hereinafter referred to as the "silica/alumina ratio") is preferably in a range of 10 to 200, more 5 preferably 15 to 100, yet more preferably 20 to 60. [0037] Moreover, the carrier preferably contains 0.1 to 80 mass% of the crystalline zeolite, and 0.1 to 60 mass% of the heat-resistant amorphous metal oxide. [0038] The catalyst carrier can be manufactured by molding a mixture 10 comprising the above solid acid and a binder, and then firing. The proportion of the solid acid is preferably in a range of 1 to 70 mass%, more preferably 2 to 60 mass%, based on the whole amount of the carrier. Moreover, in the case that the carrier contains a USY zeolite, the content of the USY zeolite is preferably in a range of 0.1 to 10 15 mass%, more preferably 0.5 to 5 mass%, based on the whole amount of the carrier. Furthermore, in the case that the carrier contains a USY zeolite and alumina-boria, the mass ratio between the USY zeolite and the alumina-boria (USY zeolite/alumina-boria) is preferably in a range of 0.03 to 1. Moreover, in the case that the carrier contains a USY 20 zeolite and silica-alumina, the mass ratio between the USY zeolite and the silica-alumina (USY zeolite/silica-alumina) is preferably in a range of 0.03 to 1. [0039] There are no particular limitations on the binder, but alumina, silica, silica-alumina, titania, or magnesia is preferable, alumina being 25 particularly preferable. The content of the binder is preferably in a range of 20 to 98 mass%, more preferably 30 to 96 mass%, based on the 12 FPO6-0521-00 whole amount of the carrier. [0040] The firing temperature of the mixture is preferably in a range of 400 to 550 oC, more preferably 470 to 530 oC, yet more preferably 490 to 530 oC. 5 [0041] Specific examples of the group VIII metal include cobalt, nickel, rhodium, palladium, iridium, and platinum. Of these, it is preferable to use one metal selected from nickel, palladium and platinum alone, or a plurality thereof in combination. [0042] Such metal can be supported on the carrier through an ordinary 10 method such as impregnation or ion exchange. There are no particular limitations on the amount of the metal supported, but the total amount of the metal is preferably in a range of 0.1 to 3.0 mass% relative to the carrier. [0043] The hydrorefining of the middle fraction can be carried out 15 under the following reaction conditions. The hydrogen partial pressure is, for example, in a range of 0.5 to 12 MPa, preferably 1.0 to 5.0 MPa. The liquid hourly space velocity (LHSV) of the middle fraction is, for example, in a range of 0.1 to 10.0 h- 1 , preferably 0.3 to 3.5 h 1 . There are no particular limitations on the hydrogen/oil ratio, but this ratio is, 20 for example, in a range of 50 to 1000 NL/L, preferably 70 to 800 NL/L. [0044] Note that, in the present specification, the "LHSV (liquid hourly space velocity)" means the volumetric flow rate of the starting material oil in a standard state (25 oC, 101325 Pa) per unit volume of the catalyst layer in which the catalyst is packed, the unit "h ' ' thereof indicating the 25 reciprocal of time (hours). Moreover, the unit "NL" of the hydrogen volume in the hydrogen/oil ratio indicates the hydrogen volume (L) in a 13 FPO6-0521-00 normal state (0 oC, 101325 Pa). [0045] Moreover, the reaction temperature in the hydrorefining is, for example, in a range of 180 to 400 'C, preferably 200 to 370 oC, more preferably 250 to 350 oC, yet more preferably 280 to 350 'C. It is 5 undesirable for the reaction temperature in the hydrorefining to exceed 370 oC, since then a side reaction of cracking into a naphtha fraction will increase, and hence the yield of the middle fraction will decrease excessively, and moreover the product will become colored, and thus there will be limitations on use as a fuel base. Furthermore, it is 10 undesirable for the reaction temperature to be less than 200 oC, since then alcohols will not be completely removed but rather will remain. [0046] Moreover, in the present embodiment, the middle fraction is preferably hydrorefined such that the content (mass%) of hydrocarbons of boiling point not more than 150 oC in the middle fraction after the 15 contact with the catalyst is 3 to 9 mass% greater than before the contact with the catalyst. [0047] The content (mass%) of hydrocarbons of boiling point not more than 150 oC in the middle fraction before and after the contact with the catalyst can be determined, for example, through analysis using a 20 publicly known method such as gas chromatography on samples taken from the inlet and the outlet of the reaction column. [0048] In the hydrocarbon oil manufacturing method of the present embodiment, reaction conditions at which the content (mass%) of hydrocarbons of boiling point not more than 150 oC in the middle 25 fraction is 3 to 9 mass% greater after the contact than before the contact with the catalyst may be determined in advance while checking the 14 FPO6-0521-00 content of hydrocarbons having each number of carbon atoms in the middle fraction before and after the contact with the catalyst using a method as above, the hydrorefining then being carried out under these conditions. 5 [0049] (Hydrotreating of heavy wax component) In the hydrotreating apparatus 30, the heavy wax component obtained from the first distillation column 10 is hydrotreated. As the hydrotreating apparatus 30, a publicly known fixed bed reaction column can be used. In the present embodiment, in the reaction column, a 10 predetermined hydrocracking catalyst is packed into the fixed bed flow reactor, so that the wax component obtained from the first distillation column 10 is hydrocracked. Here, in the hydrotreating of the wax component, chemical reaction accompanied by a reduction in molecular weight mainly proceeds, but hydroisomerization is also included under 15 the hydrotreating. [0050] An example of the hydrocracking catalyst is one in which a metal belonging to group VIII of the periodic table is supported as an active metal on a carrier containing a solid acid. [0051] A suitable carrier is one containing at least one solid acid 20 selected from crystalline zeolites such as ultrastable Y (USY) zeolites, HY zeolites, mordenite and 13 zeolites, and heat-resistant amorphous metal oxides such as silica-alumina, silica-zirconia, and alumina-boria. Furthermore, the carrier is more preferably one containing a USY zeolite, and at least one solid acid selected from silica-alumina, 25 alumina-boria and silica-zirconia, yet more preferably one containing a USY zeolite and silica-alumina. 15 FPO6-0521-00 [0052] Such a USY zeolite is a Y zeolite that has been ultrastabilized through hydrothermal treatment and/or acid treatment, whereby in addition to a microporous structure of micropores of size not more than 20 A originally possessed by the Y zeolite, new pores of size in a range 5 of 20 to 100 A are also formed. In the case of using a USY zeolite in the carrier of the hydrocracking catalyst, there are no particular limitations on the mean particle diameter thereof, but this mean particle diameter is preferably not more than 1.0 pm, more preferably not more than 0.5 pam. Moreover, for the USY zeolite, the silica/alumina molar 10 ratio (the molar ratio of silica to alumina, hereinafter referred to as the "silica/alumina ratio") is preferably in a range of 10 to 200, more preferably 15 to 100, yet more preferably 20 to 60. [0053] Moreover, the carrier preferably contains 0.1 to 80 mass% of the crystalline zeolite, and 0.1 to 60 mass% of the heat-resistant amorphous 15 metal oxide. [0054] The catalyst carrier can be manufactured by molding a mixture comprising the above solid acid and a binder, and then firing. The proportion of the solid acid is preferably in a range of 1 to 70 mass%, more preferably 2 to 60 mass%, based on the whole amount of the 20 carrier. Moreover, in the case that the carrier contains a USY zeolite, the content of the USY zeolite is preferably in a range of 0.1 to 10 mass%, more preferably 0.5 to 5 mass%, based on the whole amount of the carrier. Furthermore, in the case that the carrier contains a USY zeolite and alumina-boria, the mass ratio between the USY zeolite and 25 the alumina-boria (USY zeolite/alumina-boria) is preferably in a range of 0.03 to 1. Moreover, in the case that the carrier contains a USY 16 FPO6-0521-00 zeolite and silica-alumina, the mass ratio between the USY zeolite and the silica-alumina (USY zeolite/silica-alumina) is preferably in a range of 0.03 to 1. [0055] There are no particular limitations on the binder, but alumina, 5 silica, silica-alumina, titania, or magnesia is preferable, alumina being particularly preferable. The content of the binder is preferably in a range of 20 to 98 mass%, more preferably 30 to 96 mass%, based on the whole amount of the carrier. [0056] The firing temperature of the mixture is preferably in a range of 10 400 to 550 oC, more preferably 470 to 530 oC, yet more preferably 490 to 530 oC. [0057] Specific examples of the group VIII metal include cobalt, nickel, rhodium, palladium, iridium, and platinum. Of these, it is preferable to use one metal selected from nickel, palladium and platinum alone, or a 15 plurality thereof in combination. [0058] Such metal can be supported on the carrier through an ordinary method such as impregnation or ion exchange. There are no particular limitations on the amount of the metal supported, but the total amount of the metal is preferably in a range of 0.1 to 3.0 mass% relative to the 20 carrier. [0059] The hydrocracking of the heavy wax component can be carried out under the following reaction conditions. The hydrogen partial pressure is, for example, in a range of 0.5 to 12 MPa, preferably 1.0 to 5.0 MPa. The liquid hourly space velocity (LHSV) of the middle 25 fraction is, for example, in a range of 0.1 to 10.0 h -1 , preferably 0.3 to 3.5 h'. There are no particular limitations on the hydrogen/oil ratio, 17 FPO6-0521-00 but this ratio is, for example, in a range of 50 to 1000 NL/L, preferably 70 to 800 NL/L. [0060] Moreover, in the present embodiment, the wax component is preferably hydrocracked such that the content of a fraction of boiling 5 point not more than 360 oC in the wax component after the contact with the catalyst is in a range of 45 to 85 mass%. [0061] The content of the fraction of boiling point not more than 360 oC in the wax component after the contact with the catalyst can be determined, for example, through analysis using a publicly known 10 method such as gas chromatography on samples taken from the inlet and the outlet of the reaction column. [0062] In the hydrocarbon oil manufacturing method of the present embodiment, reaction conditions at which the content of the fraction of boiling point not more than 360 oC in the wax component after the 15 contact with the catalyst is 45 to 85 mass% may be determined in advance, the hydrocracking then being carried out under these conditions. [0063] (Fractionation of hydrocarbon oil) The hydrotreated middle fraction flowing out from the hydrotreating 20 apparatus 20 (hereinafter sometimes referred to as the "hydrorefmining product", and the hydrotreated wax component flowing out from the hydrotreating apparatus 30 (hereinafter sometimes referred to as the "hydrocracking product") are transported into the second distillation column 40 via the gas-liquid separation tanks 22 and 32 respectively, 25 and distilled together in the second distillation column 40, so as to be fractionated into desired fractions. 18 FPO6-0521-00 [0064] In the gas-liquid separation tanks 22 and 32, the hydrorefining product and the hydrocracking product are each separated into, for example, unreacted hydrogen gas and light hydrogen gas comprising hydrocarbons having not more than 4 carbon atoms, and a liquid 5 hydrocarbon oil comprising hydrocarbons having not less than 5 carbon atoms. Here, the liquid hydrocarbon oils are transferred into the distillation column 40 as the hydrorefmning product and the hydrocracking product. As each of the gas-liquid separation tanks, a publicly known one can be used. 10 [0065] In the second distillation column 40, two cut points are set when fractionating the hydrorefining product and the hydrocracking product, whereby a fraction having a boiling point of not more than the first cut point can be obtained as a light fraction, a fraction having a boiling point between the first cut point and the second cut point as a middle 15 fraction, and a fraction having a boiling point of not less than the second cut point as a bottom oil (the heavy wax component). In the present embodiment, the middle fraction, which is fractionated such that the content of a fraction of boiling point 150 to 360 'C is not less than 90 mass% and the content of a fraction of boiling point not less than 20 350 oC is not less than 5 mass%, is obtained as the hydrocarbon oil according to the present invention. [0066] The first cut point and the second cut point are preferably set in a range of 135 to 170 oC and in a range of 345 to 375 'C respectively, more preferably in a range of 145 to 155 oC and in a range of 360 to 25 375 oC respectively. [0067] Note that the number of cut points for the second distillation 19 FPO6-0521-00 column 40 is not limited to being two, but rather three or more may be set so long as the hydrocarbon oil according to the present invention can be obtained as described above. [0068] The middle fraction obtained as described above, i.e. the 5 hydrocarbon oil according to the present invention, is recovered via the recovery flow path 8. Moreover, a naphtha fraction lighter than the middle fraction is discharged out of the system via the flow path 7, while a wax component heavier than the middle fraction is supplied into the hydrotreating apparatus 30 via the circulating flow path 9, and 10 subjected to the hydrocracking as required. [0069] According to the hydrocarbon oil manufacturing method of the present invention described above, a hydrocarbon oil having a pour point of not more than -7.5 oC and a kinematic viscosity at 30 oC of not less than 2.5 mm 2 /s can be obtained with high yield. Such a 15 hydrocarbon oil can be suitably used as, for example, a base for an environmentally-friendly diesel fuel. EXAMPLES [0070] Following is a more detailed description of the present invention through working examples. However, the present invention is not 20 limited to these working examples. [0071] <Preparation of catalyst> (Catalyst A) A USY zeolite (silica/alumina molar ratio: 37) having a mean particle diameter of 1.1 lim, silica-alumina (silica/alumina molar ratio: 14), and 25 an alumina binder were mixed and kneaded together in a weight ratio of 3:57:40, and the mixture was molded into cylindrical shapes of diameter 20 FPO6-0521-00 approximately 1.6 mm and length approximately 4 mm, and then firing was carried out at 500 oC for 1 hour, whereby a carrier was obtained. A chloroplatinic acid aqueous solution was impregnated into the carrier, thus supporting platinum. The platinum-supporting carrier was dried 5 at 120 oC for 3 hours, and then fired at 500 'C for 1 hour, whereby catalyst A was obtained. The amount of platinum supported was 0.8 mass% relative to the carrier. [0072] <Manufacture of hydrocarbon oil for diesel fuel base stock > (Example 1) 10 (Fractionation of FT synthetic oil) A produced oil obtained through FT synthesis (an FT synthetic oil) (content of hydrocarbons of boiling point not less than 150 oC: 84 mass%, content of hydrocarbons of boiling point not less than 360 oC: 42 mass%, both contents based on total amount of FT synthetic oil (total 15 amount of hydrocarbons having not less than 5 carbon atoms)) was separated using a distillation column into a light fraction of boiling point not more than 150 oC, a middle fraction of boiling point 150 to 350 oC (content of hydrocarbons of boiling point 150 to 360 oC: 100 mass%, content of hydrocarbons of boiling point not less than 350 oC: 0 20 mass%, content of hydrocarbons of boiling point 300 to 350 oC: 19 mass%, content of hydrocarbons of boiling point not more than 150 oC: 0 mass%), and a column bottom residue heavy wax component (being a fraction of boiling point not less than 350 oC). [0073] (Hydrotreating (hydrorefining) of middle fraction) 25 Catalyst A (150 ml) was packed into a fixed bed flow reactor, the middle fraction obtained as described above was supplied in at a rate of 21 FPO6-0521-00 300 ml/h from the top of the reaction column, and hydrotreating was carried out under a hydrogen gas stream under the following reaction conditions. [0074] That is, hydrogen was supplied in from the top of the column at 5 a hydrogen/oil ratio of 340 NL/L relative to the middle fraction, a back pressure valve was adjusted such that the reaction column pressure was fixed at an inlet pressure of 3.0 MPa, and under these conditions the reaction temperature (catalyst bed weight average temperature) was adjusted such that the content of hydrocarbons of boiling point not more 10 than 150 oC in the hydrotreated middle fraction (the reaction product) was 5 mass%. The reaction temperature for this was 308 oC. The above content was checked through gas chromatography measurement on the hydrotreated middle fraction (the reaction product). [0075] (Hydrotreating (hydrocracking) of heavy wax component) 15 On the other hand, using another reaction column, catalyst A (150 ml) was packed into a fixed bed flow reactor, the column bottom residue heavy wax component obtained as described above was supplied in at a rate of 300 ml/h from the top of the reaction column, and hydrotreating was carried out under a hydrogen gas stream under the following 20 reaction conditions. [0076] That is, hydrogen was supplied in from the top of the column at a hydrogen/oil ratio of 680 NL/L relative to the wax component, a back pressure valve was adjusted such that the reaction column pressure was fixed at an inlet pressure of 4.0 MPa, and under these conditions the 25 reaction temperature (catalyst bed weight average temperature) was adjusted such that the total content of cracking products of boiling point 22 FPO6-0521-00 not more than 360 oC in the hydrotreated wax component (the hydrocracking product) was approximately 70 mass%. The reaction temperature for this was 320 oC. The above content was checked through gas chromatography measurement on the hydrotreated wax 5 component (the hydrocracking product) and analysis of the distillation characteristics. [0077] (Fractionation of hydrorefining product and hydrocracking product) The middle fraction hydrorefining product and the wax component 10 hydrocracking product obtained as described above were mixed together as is in the proportion of their respective yields, and the mixture was fractionated using a distillation column. A fraction of boiling point 150 to 360 oC was obtained as a hydrocarbon oil for a diesel fuel base stock of Working Example 1. For the hydrocarbon oil obtained, the 15 pour point (oC) and the kinematic viscosity at 30 oC (mm 2 /s) were measured. The results are shown in Table 1. The pour point was measured in accordance with the test method of JIS K2269, and the kinematic viscosity at 30 oC was measured in accordance with the test method of JIS K2283. 23 FPO6-0521-00 [0078] Table 1 Example Example Example Example Example Comparative Comparative 1 2 3 4 5 Example 1 Example 2 Content of fraction of boiling point not less than 350 oC in middle 0 0 0 0 4 10 20 fraction to be subjected to hydrotreating (mass%) Boiling point range of 150- 150- 145- 140- 150 hydrocarbon oil 360 380 380 385 360 150 - 360 150 - 360 fodiseful 360 380 380 385 360 for diesel fuel base stock (°C) Content of fraction of boiling point 150 to 360 OC in 99 93 90 86 99 99 99 hydrocarbon oil for diesel fuel base stock (mass%) Content of fraction of boiling point not less than 350 oC lessthan350C 5 8 7.8 9 8 8 13 in hydrocarbon oil for diesel fuel base stock (mass%) Yield of hydrocarbon oil for diesel fuel base stock 64 68 70 72 65 63 65 relative to starting material FT synthetic oil (mass%) Kinematic viscosity of hydrocarbon oil 2.6 2.8 2.7 2.7 2.65 2.8 3.0 for diesel fuel base stock at 30 °C (mm 2 /s) Pour point of hydrocarbon oil -12.5 -7.5 -10.0 -7.5 -10.0 -5.0 -2.5 for diesel fuel base stock (oC) 24 FPO6-0521-00 [0079] (Example 2) A hydrocarbon oil for a diesel fuel base stock of Example 2 was obtained as in Example 1, except that instead of obtaining a fraction of boiling point 150 to 360 oC as the hydrocarbon oil for a diesel fuel base 5 stock through the fractionation of the hydrorefining product and the hydrocracking product as in Example 1, a fraction of boiling point 150 to 380 oC was obtained as the hydrocarbon oil for a diesel fuel base stock. For the hydrocarbon oil obtained, analysis was carried out as in Example 1. The results are shown in Table 1. 10 [0080] (Example 3) A hydrocarbon oil for a diesel fuel base stock of Example 3 was obtained as in Example 1, except that instead of obtaining a fraction of boiling point 150 to 360 oC as the hydrocarbon oil for a diesel fuel base stock through the fractionation of the hydrorefming product and the 15 hydrocracking product as in Example 1, a fraction of boiling point 145 to 380 oC was obtained as the hydrocarbon oil for a diesel fuel base stock. For the hydrocarbon oil obtained, analysis was carried out as in Example 1. The results are shown in Table 1. [0081] (Example 4) 20 A hydrocarbon oil for a diesel fuel base stock of Example 4 was obtained as in Example 1, except that instead of obtaining a fraction of boiling point 150 to 360 oC as the hydrocarbon oil for a diesel fuel base stock through the fractionation of the hydrorefining product and the hydrocracking product as in Example 1, a fraction of boiling point 140 25 to 385 oC was obtained as the hydrocarbon oil for a diesel fuel base stock. For the hydrocarbon oil obtained, analysis was carried out as in 25 FPO6-0521-00 Example 1. The results are shown in Table 1. [0082] (Example 5) A hydrocarbon oil for a diesel fuel base stock of Example 5 was obtained as in Example 1, except that instead of obtaining a fraction of 5 boiling point 150 to 350 oC as the middle fraction through the fractionation of the FT synthetic oil as in Example 1, a fraction of boiling point 150 to 356 oC (content of hydrocarbons of boiling point not less than 350 oC: 4 mass%) was obtained, and a wax component being a fraction of boiling point not less than 356 'C was obtained as 10 the column bottom residue wax component. For the hydrocarbon oil obtained, analysis was carried out as in Example 1. The results are shown in Table 1. [0083] (Comparative Example 1) A hydrocarbon oil for a diesel fuel base stock of Comparative Example 15 1 was obtained as in Example 1, except that instead of obtaining a fraction of boiling point 150 to 350 oC as the middle fraction through the fractionation of the FT synthetic oil as in Example 1, a fraction of boiling point 150 to 362 oC (content of hydrocarbons of boiling point not less than 350 oC: 10 mass%) was obtained, and a wax component 20 being a fraction of boiling point not less than 362 'C was obtained as the column bottom residue wax component. For the hydrocarbon oil obtained, analysis was carried out as in Example 1. The results are shown in Table 1. [0084] (Comparative Example 2) 25 A hydrocarbon oil for a diesel fuel base stock of Comparative Example 2 was obtained as in Example 1, except that instead of obtaining a 26 FPO6-0521-00 fraction of boiling point 150 to 350 oC as the middle fraction through the fractionation of the FT synthetic oil as in Example 1, a fraction of boiling point 150 to 375 oC (content of hydrocarbons of boiling point not less than 350 oC: 20 mass%) was obtained, and a wax component 5 being a fraction of boiling point not less than 375 oC was obtained as the column bottom residue wax component. For the hydrocarbon oil obtained, analysis was carried out as in Example 1. The results are shown in Table 1. [0085] (Comparative Example 3) 10 A hydrocarbon oil for a diesel fuel base stock of Comparative Example 3 was obtained as in Example 1, except that instead of obtaining a fraction of boiling point 150 to 360 'C as the hydrocarbon oil for a diesel fuel base stock through the fractionation of the hydrorefming product and the hydrocracking product as in Example 1, a fraction of 15 boiling point 180 to 330 oC was obtained as the hydrocarbon oil for a diesel fuel base stock. For the hydrocarbon oil obtained, analysis was carried out as in Example 1. The results are shown in Table 2. 27 FPO6-0521-00 [0086] Table 2 Comparative Comparative Example 3 Example 4 Boiling point range of hydrocarbon oil for diesel 180 - 330 150 - 370 fuel base stock (oC) Content of fraction of boiling point 150 to 100 96 360 oC in hydrocarbon oil for diesel fuel base stock (mass/o%) Content of fraction of boiling point not less than 0 11 350 C in hydrocarbon oil for diesel fuel base stock (mass%) Yield of hydrocarbon oil for diesel fuel base 46 24 stock relative to starting material FT synthetic oil (mass%) Kinematic viscosity of hydrocarbon oil for 2.6 2.6 diesel fuel base stock at 30 °C (mm2/s) Pour point of hydrocarbon oil for diesel fuel -7.5 -15 base stock (oC) II [0087] (Comparative Example 4) A hydrocarbon oil for a diesel fuel base stock of Comparative Example 4 was obtained as in Example 1, except that the middle fraction was not 5 used as in Example 1, but rather only the hydrocracking product from the column bottom residue wax component was fractionated using the distillation column, a fraction of boiling point 150 to 370 oC being obtained as the hydrocarbon oil for a diesel fuel base stock. For the hydrocarbon oil obtained, analysis was carried out as in Example 1. 10 The results are shown in Table 2. 28

Claims (6)

1. A hydrocarbon oil manufacturing method, comprising the steps of: fractionating a synthetic oil obtained through Fischer-Tropsch synthesis, 5 so as to obtain a middle fraction having a content of a fraction of boiling point 150 to 360 oC of not less than 90 mass% and a content of a fraction of boiling point not less than 350 oC of not more than 5 mass%, and a wax component that is heavier than said middle fraction; and bringing each of said middle fraction and said wax component into 10 contact with a hydrotreating catalyst in the presence of hydrogen, and then mixing together, and fractionating, so as to obtain a hydrocarbon oil having a content of a fraction of boiling point 150 to 360 oC of not less than 86 mass% and a content of a fraction of boiling point not less than 350 oC of not less than 5 mass%. 15
2. The hydrocarbon oil manufacturing method according to claim 1, wherein said middle fraction is hydrotreated such that the content of hydrocarbons of boiling point not more than 150 'C in said middle fraction is 3 to 9 mass% greater after the contact than before the contact with said hydrotreating catalyst. 20
3. The hydrocarbon oil manufacturing method according to claim 1 or 2, wherein said wax component is hydrotreated such that the content of a fraction of boiling point not more than 360 oC in said wax component after the contact with said hydrotreating catalyst is 45 to 85 mass%. 25
4. The hydrocarbon oil manufacturing method according to any one of claims 1 to 3, wherein each of said hydrotreating catalyst brought 29 FPO6-0521-00 into contact with said middle fraction and said hydrotreating catalyst brought into contact with said wax component comprises a carrier containing 0.1 to 80.0 mass% of a crystalline zeolite and 0.1 to 60.0 mass% of a heat-resistant amorphous metal oxide, and at least one metal 5 selected from the group consisting of metals belonging to group VIII of the periodic table supported on said carrier.
5. The hydrocarbon oil manufacturing method according to any one of claims 1 to 4, wherein said middle fraction is brought into contact with said hydrotreating catalyst at a reaction temperature of 200 10 to 370 oC, a hydrogen partial pressure of 1.0 to 5.0 MPa, and a liquid hourly space velocity of 0.3 to 3.5 h', and said wax component is brought into contact with said hydrotreating catalyst at a reaction temperature of 200 to 370 oC, a hydrogen partial pressure of 1.0 to 5.0 MPa, and a liquid hourly space velocity of 0.3 to 3.5 hW. 15
6. A hydrocarbon oil obtained through the manufacturing method according to any of claims 1 to 5, having a pour point of not more than 7.5 oC, and a kinematic viscosity at 30 oC of not less than 2.5 mm2/s. 30
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