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
  • C10G47/00—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions
• • C—CHEMISTRY; METALLURGY
  • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
  • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
  • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
  • C10G2300/10—Feedstock materials
  • C10G2300/1022—Fischer-Tropsch products

Definitions

• the present invention relates to a method for hydrotreating synthetic oil, and more particularly to a method for hydrotreating synthetic oil obtained by the Fischer-Tropsch synthesis method.
• the present invention also relates to a method for producing a fuel substrate.
• FT synthetic oil t ⁇ ⁇
• an oxygen-containing compound such as alcohol having a high normal paraffin content
• the synthetic oil has an insufficient octane number for use as automobile gasoline, and low-temperature fluidity for use as diesel fuel.
• oxygen-containing compounds such as alcohol adversely affect the oxidation stability of the fuel. Therefore, FT synthetic oil is used as a fuel base after being subjected to hydrogenation treatment to convert normal paraffin in the synthetic oil into isoparaffin or oxygen-containing compounds into other substances. Is common.
• Patent Document 1 Pamphlet of International Publication No. OOZ020535
• Patent Document 2 French Patent Publication No. 2826971 Specification
• the source of diesel fuel base material in FT synthetic oil is a heavy wax component (particularly, a fraction having a boiling point of 360 ° C or higher) and a middle fraction (particularly, a boiling point of 150 to 360).
• the fuel base obtained by hydrocracking the wax content is excellent in fluidity, the amount of FT synthetic oil that can be produced is limited, and it is used for applications such as lubricating oil. In some cases, a sufficient amount of fuel base material cannot always be secured.
• Patent Document 2 even if the technique described in Patent Document 2 is used, it is difficult to achieve the low temperature fluidity required for diesel fuel base materials simply by hydroisomerizing the middle fraction of FT synthetic oil.
• the yield of middle distillate is greatly impaired in the case where the light soot treatment is involved.
• the present inventors diligently studied, and as a result, the FT synthetic oil hydrocracked by bringing a FT synthetic oil containing a specific amount of a specific fraction into contact with a hydrocracking catalyst.
• the reaction conditions are set using the specific hydrocarbon content as an index, the middle point cloud point obtained is greatly reduced even though the middle distillate loss is sufficiently suppressed.
• the present invention has been completed. That is, the method for hydrotreating a synthetic oil of the present invention is a synthesis obtained by a Fischer-Tropsch synthesis method in the presence of hydrogen and having a hydrocarbon content of 9 to 21 carbon atoms of 90% by mass or more.
• the hydrocracking catalyst is brought into contact with the oil and the synthetic oil so that the content (mass%) of hydrocarbons having 8 or less carbon atoms in the synthetic oil after contact is 3 to 9 mass% higher than that before the contact. Is hydrocracked.
• the low-temperature fluidity of the middle distillate can be sufficiently improved while sufficiently maintaining the yield of the middle distillate obtained from the synthetic oil. Furthermore, according to the method for hydrotreating synthetic oil of the present invention, oxygen-containing compounds such as alcohol can be sufficiently reduced. In addition, according to the present invention, it is possible to reform the FT synthetic oil to be useful as a diesel fuel base material only by hydrotreating the middle distillate of the FT synthetic oil. It becomes possible to do.
• the content (mass%) of hydrocarbons having 8 or less carbon atoms in the synthetic oil after contact is 3 to 9 mass% greater than that before contact.
• the synthetic oil has a hydrocarbon content of 9 to 14 carbon atoms of 70 mass% or less, and the synthetic oil after contact has 9 carbon atoms.
• ⁇ 14 hydrocarbon content (mass%) is 2 mass% or more higher than that before contact, and the content of hydrocarbons with 15 to 21 carbon atoms in the synthetic oil after contact (mass%) It is preferred to hydrocrack the synthetic oil so that is less than 2% by mass below that before contact.
• the hydrocracking catalyst is selected from the group consisting of ultra-stabilized Y-type zeolite, silica-alumina, alumina-polya, and silica-zircoua1. It is preferable that it contains at least one metal selected from the group consisting of a carrier containing at least one kind and a metal belonging to Group VIII of the periodic table supported on the carrier.
• the reaction temperature when contacting the synthetic oil and the hydrocracking catalyst is 200 to 370 ° C
• the hydrogen partial pressure is 1.0 to 5 . ompA
• one or, it is preferable liquid hourly space velocity is 0. 3 ⁇ 3. 5h _ 1.
• the method for producing a fuel base material of the present invention includes a synthetic oil obtained by a Fischer-Tropsch synthesis method in the presence of hydrogen and having a hydrocarbon content of 9 to 21 carbon atoms of 90% by mass or more.
• the hydrocracking catalyst is brought into contact with the synthetic oil so that the content (mass%) of hydrocarbons having 8 or less carbon atoms in the synthetic oil after contact is 3 to 9 mass% higher than that before the contact.
• the present invention even when the middle fraction of synthetic oil obtained by the FT synthesis method is processed, the low-temperature fluidity of the middle fraction is sufficiently maintained while the yield of the middle fraction is sufficiently maintained.
• a method for hydrotreating synthetic oil that can be improved can be provided.
• FIG. 1 is a flowchart showing an example of a fuel production apparatus suitable for carrying out a method for producing an environmentally low load fuel according to the present invention.
• the method for hydrotreating a synthetic oil of the present invention comprises a synthetic oil obtained by a Fischer-Tropsch synthesis method in the presence of hydrogen and having a hydrocarbon content of 9 to 21 carbon atoms of 90% by mass or more. Hydrogenate the synthetic oil so that the content (mass%) of hydrocarbons with 8 or less carbon atoms in the synthetic oil after contact with the hydrocracking catalyst is 3-9 mass% higher than that before the contact. It is characterized by decomposing.
• the synthetic oil used in the method for hydrotreating a synthetic oil of the present invention includes a hydrocarbon content of 9 to 21 carbon atoms obtained by fractionating a product oil having a Fischer-Tropsch synthesis method.
• An intermediate fraction for example, a fraction having a boiling point of 150 to 360 ° C.
• N 90% by mass or more
• Examples of the hydrocracking catalyst include a catalyst comprising a solid acid-containing carrier and a metal belonging to Group VIII of the periodic table as an active metal.
• Suitable supports include those comprising one or more kinds of solid acids selected from among super-stabilized Y-type (USY) zeolite, silica alumina, silica zircoa and alumina polya. Further, it is more preferable that the carrier comprises USY zeolite and one or more kinds of solid acids selected from silica alumina, alumina polya and silica zirconia. USY zeolite It is more preferable that the material is composed of alumina polyamide and USY zeolite and aluminaboria.
• USY zeolite is a super-stable Y-type zeolite by hydrothermal treatment and Z or acid treatment.
• 20 ⁇ New pores are formed in the range of LOOA.
• USY zeolite is used as the carrier for the hydrocracking catalyst, there is no particular limitation on the average particle size.
• the force is preferably 1.0 ⁇ m or less, more preferably 0.5 ⁇ m or less.
• silica Z alumina ratio is preferably 10 to 200 and 15 to L00. Even more preferred is 20-60.
• the catalyst carrier is formed by molding a mixture containing the solid acid and the binder and then firing the mixture. Can be manufactured.
• the blending ratio of the solid acid is preferably 1 to 70% by mass, more preferably 2 to 60% by mass based on the total amount of the carrier.
• the amount of USY zeolite is preferably 0.1 to 10% by mass based on the total amount of the carrier, and is 0.5 to 5% by mass. Is more preferred.
• the mixing ratio of USY zeolite and alumina polya is preferably 0.03 to 1.
• the mixing ratio of USY zeolite and silica alumina is preferably 0.03 to 1 in mass ratio.
• the noinder is not particularly limited, but alumina, silica, silica alumina, titanium and magnesia are preferred.
• the blending amount of the binder is preferably 20 to 98% by mass, more preferably 30 to 96% by mass based on the total amount of the carrier.
• the firing temperature of the mixture is preferably in the range of 400 to 550 ° C, more preferably in the range of 470 to 530 ° C, and more preferably in the range of 490 to 530 ° C. Is more preferable
• Group VIII metal examples include cobalt, nickel, rhodium, palladium, iridium, platinum, and the like. Among these, it is preferable to use a metal selected from nickel, palladium and platinum alone or in combination of two or more.
• metals can be supported on the above-mentioned carrier by a conventional method such as impregnation or ion exchange.
• the amount of metal to be supported is not particularly limited, but the total amount of metal is preferably 0.1 to 3.0% by mass with respect to the support.
• the configuration of the apparatus used in the method for hydrotreating synthetic oil of the present invention is not particularly limited, and may include one reaction tower or a combination of a plurality of reaction towers. There may be. In the present invention, it is preferable to perform hydrocracking of synthetic oil using a fixed bed flow reactor filled with the above-mentioned catalyst.
• Hydrocracking of synthetic oil can be performed under the following reaction conditions.
• the hydrogen partial pressure is preferably a force of 1.0 to 5 OMPa, such as 0.5 to 12 MPa.
• Synthetic oil liquid As between speeds (LHSV), 0. 1 ⁇ 10. Although Oh _1 and the like, 0. 3 to 3. 5h _1 is preferred arbitrariness.
• the hydrogen Z oil ratio is not particularly limited, but 50-: LOOONLZL is preferred, and 70-800 NLZL is preferred! / ⁇ .
• LHSV liquid hourly space velocity
• the reaction temperature in hydrocracking is preferably 200 to 370 at a force of 180 to 400 ° C, more preferably 250 to 350 ° C. Even more preferred is -35 0 ° C. If the reaction temperature in hydrocracking exceeds 370 ° C, the yield of the middle distillate will be extremely reduced, and the resulting product will be colored, which limits the use as a fuel substrate. On the other hand, when the reaction temperature is lower than 200 ° C., the alcohol content cannot be completely removed, which is not preferable.
• the synthetic oil and the synthetic oil so that the content (mass%) of the hydrocarbon having 8 or less carbon atoms in the synthetic oil after contact is 3 to 9 mass% higher than that before the contact. It is preferred to hydrocrack the synthetic oil by adjusting the reaction temperature when contacting with the hydrocracking catalyst.
• the content (mass%) of hydrocarbons having ⁇ 14 and the content (mass%) of hydrocarbons having 14 to 21 carbon atoms are, for example, gas chromatographs sampled at the inlet and outlet of the reaction tower. It can be analyzed and obtained by a known method such as a graph.
• the content of hydrocarbons of each carbon number in the synthetic oil before contact and the synthetic oil after contact are confirmed by the above-mentioned method, after contact.
• the reaction conditions in which the content (mass%) of hydrocarbons having 8 or less carbon atoms in the synthetic oil of 3 to 9 mass% is larger than that before contact may be determined in advance, and hydrocracking may be performed under these conditions .
• contact Hydrocarbons with 9 to 14 carbon atoms in the later synthetic oil are 2 mass% or more larger than those before contact, and hydrocarbons with 15 to 21 carbon atoms in the synthetic oil after contact It is also possible to predetermine reaction conditions in which the content (mass%) of the catalyst is 2 mass% or more smaller than that before contact, and perform hydrogenolysis under these conditions.
• the contacted synthetic oil (fluid) flowing out from the above reaction tower is, for example, in a gas-liquid separation tank, light hydrocarbon gas composed of unreacted hydrogen gas or hydrocarbons having 4 or less carbon atoms, and carbon number. More than 5 hydrocarbon power is separated into liquid hydrocarbon composition oil.
• the separated liquid hydrocarbon composition oil is further fractionally distilled, for example, fuel base materials such as gasoline base materials, diesel fuel base materials, kerosene base materials, light oil base materials, and aviation fuel base materials. It is used as
• the method for producing a fuel base material of the present invention is obtained by a Fischer-Tropsch synthesis method in the presence of hydrogen, a synthetic oil having a hydrocarbon content of 9 to 21 carbon atoms of 90% by mass or more, and hydrogenation.
• the hydrocracking step it is preferable that the hydrocracking of the synthetic oil is performed under the conditions in the above-described synthetic oil hydrotreating method according to the present invention.
• Examples of the middle distillate include a distillate having a boiling point in the range of 150 ° C to 360 ° C. When obtaining a diesel fuel substrate, it is preferable to obtain a fraction within the range of 150 ° C to 360 ° C as the middle fraction.
• FIG. 1 is a flowchart showing an example of a fuel base material production apparatus suitable for carrying out the fuel base material manufacturing method according to the present invention.
• a fuel production apparatus 100 shown in FIG. 1 includes a reaction tower 10 and a distillation tower 20 for distilling a reaction product obtained in the reaction tower 10.
• the reaction tower 10 is a fixed bed type reaction tower, in which a hydrocracking catalyst layer 12 containing the above hydrocracking catalyst is provided. In this reaction tower 10, the present invention described above is applied.
• the synthetic oil is hydrocracked based on the synthetic oil hydrotreating method.
• a line L1 for supplying synthetic oil into the reaction tower 10 is connected to the top of the reaction tower 10, and hydrogen is supplied to the upstream side of the connection with the reaction tower 10 in the line L1.
• Line L2 is connected.
• a line L3 for extracting a reaction product from the reaction tower 10 is connected to the bottom of the reaction tower 10, and the other end of the line L3 is connected to an atmospheric distillation device 20.
• the distillation apparatus 20 is for fractionating the reaction product produced by the reaction in the reaction tower 10 into each fraction having a specific boiling range. With the distillation apparatus 20, for example, a fraction within a range of 150 ° C. to 360 ° C. suitable as a diesel fuel substrate can be obtained. In addition, the distillation apparatus 20 converts the reaction product into a gas fraction (light hydrocarbon having 4 or less carbon atoms), a heavy naphtha fraction (fraction having a boiling point of 80 to 145 ° C), and a kerosene fraction (boiling point 145 to 260).
• a gas fraction light hydrocarbon having 4 or less carbon atoms
• a heavy naphtha fraction fraction having a boiling point of 80 to 145 ° C
• kerosene fraction boiling point 145 to 260
• USY zeolite with a mean particle size of 0.9 ⁇ m (silica Z-alumina molar ratio: 37), silica alumina (silica Z-alumina molar ratio: 14) and alumina binder were mixed and kneaded at a weight ratio of 3:57:40.
• This carrier was impregnated with an aqueous chloroplatinic acid solution to carry platinum. This was dried at 120 ° C. for 3 hours and then calcined at 500 ° C. for 1 hour to obtain Catalyst 1.
• Catalyst 1 except that alumina polya was used instead of silica alumina in catalyst 1.
• the catalyst 2 was prepared in the same manner as described above by molding the carrier, firing the metal, drying, and firing.
• catalyst 1 instead of the chloroplatinic acid aqueous solution in catalyst 1, the support was impregnated with a chloroplatinic acid aqueous solution and a palladium chloride aqueous solution, and the supported amounts of platinum and palladium were 0.7% by mass and 0.1% by mass, respectively, with respect to the support. Except for the above, catalyst 3 was prepared in the same manner as catalyst 1, except that the carrier was molded and calcined, supported with metal, dried and calcined.
• 9 to 21 carbon atoms (boiling point 150 to 360 ° C) obtained by filling catalyst 1 (150 ml) into a fixed bed flow reactor and fractionating oil synthesized by the FT synthesis method as a raw material Synthetic oil having a hydrocarbon content of 100 mass% and a hydrocarbon content of 9 to 14 carbon atoms (boiling point 150 to 250 ° C) of 45 mass% (normal paraffin content of 9 to 21 carbon atoms: 90% by mass, alcohol content : 5 % by mass, olefin content: 5% by mass (based on the total mass of raw materials)) (hereinafter sometimes referred to as “raw synthetic oil”) at a rate of 300 mlZh Then, hydrogenation was performed under a hydrogen stream under the following reaction conditions.
• the hydrolyzed synthetic oil (reaction product) is subjected to precision distillation to obtain a carbon number of 9 A fraction with a hydrocarbon power of ⁇ 21 (boiling point boiling 150-360 ° C.) was obtained and the cloud point was measured.
• the raw synthetic oil was subjected to precision distillation to obtain a fraction composed of hydrocarbons having 9 to 21 carbon atoms (fraction having a boiling point of 150 to 360 ° C), and the cloud point was also measured.
• the cloud point was measured using an automatic pour point / cloud point tester (manufactured by Tanaka Scientific Instruments Manufacturing Co., Ltd., MPC-101A).
• Table 1 shows the results obtained from the above analysis.
• the content of each component in the table is based on the total amount of synthetic oil.
• the hydrogenation treatment was performed in the same manner as in Example 1 except that the catalyst 2 was used instead of the catalyst 1 in Example 1.
• the reaction temperature (catalyst bed weight average temperature) was adjusted in the same manner as in Example 1 so that the content of hydrocarbons having 8 or less carbon atoms in the synthetic oil (reaction product) after contact was 7% by mass.
• the result was 308 ° C.
• the obtained contacted synthetic oil (reaction product) was analyzed in the same manner as in Example 1. The results obtained are shown in Table 1.
• the hydrogenation treatment was performed in the same manner as in Example 1 except that the catalyst 3 was used instead of the catalyst 1 in Example 1.
• the reaction temperature (catalyst bed weight average temperature) is the same as in Example 1 and the content of hydrocarbons having 8 or less carbon atoms in the synthetic oil (reaction product) after contact is as follows: The temperature was adjusted to 308 ° C.
• the obtained synthetic oil (reaction product) after contact was analyzed in the same manner as in Example 1. The results obtained are shown in Table 1.
• the present invention even when the middle distillate of synthetic oil obtained by the FT synthesis method is processed, the low-temperature fluidity of the middle distillate is sufficiently maintained while the yield of the middle distillate is sufficiently maintained.
• a method for hydrotreating synthetic oil that can be improved can be provided.

Landscapes

• 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)
• Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
• Catalysts (AREA)

Priority Applications (2)

Applications Claiming Priority (2)

Publications (1)

Family

ID=38371385

Family Applications (1)

Country Status (6)

Cited By (1)

Families Citing this family (3)

Citations (6)

Family Cites Families (1)

• 2006
  • 2006-02-13 JP JP2006035638A patent/JP4848191B2/ja not_active Expired - Fee Related
• 2007
  • 2007-02-06 RU RU2008136837/04A patent/RU2419649C2/ru not_active IP Right Cessation
  • 2007-02-06 CN CN200780005375.5A patent/CN101384686B/zh not_active Expired - Fee Related
  • 2007-02-06 MY MYPI20082907 patent/MY148282A/en unknown
  • 2007-02-06 AU AU2007216008A patent/AU2007216008B9/en not_active Ceased
  • 2007-02-06 WO PCT/JP2007/051990 patent/WO2007094199A1/ja active Application Filing

Patent Citations (6)

Also Published As

Similar Documents

Legal Events