WO2007114001A1 - ワックスの水素化分解方法 - Google Patents
ワックスの水素化分解方法 Download PDFInfo
- Publication number
- WO2007114001A1 WO2007114001A1 PCT/JP2007/054926 JP2007054926W WO2007114001A1 WO 2007114001 A1 WO2007114001 A1 WO 2007114001A1 JP 2007054926 W JP2007054926 W JP 2007054926W WO 2007114001 A1 WO2007114001 A1 WO 2007114001A1
- Authority
- WO
- WIPO (PCT)
- Prior art keywords
- mass
- wax
- hydrocracking
- fraction
- boiling point
- Prior art date
Links
Classifications
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J29/00—Catalysts comprising molecular sieves
- B01J29/04—Catalysts comprising molecular sieves having base-exchange properties, e.g. crystalline zeolites
- B01J29/06—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof
- B01J29/08—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y
- B01J29/10—Crystalline aluminosilicate zeolites; Isomorphous compounds thereof of the faujasite type, e.g. type X or Y containing iron group metals, noble metals or copper
- B01J29/12—Noble metals
- B01J29/126—Y-type faujasite
-
- 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
- C10G47/02—Cracking of hydrocarbon oils, in the presence of hydrogen or hydrogen- generating compounds, to obtain lower boiling fractions characterised by the catalyst used
- C10G47/10—Cracking 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
- C10G47/12—Inorganic carriers
- C10G47/16—Crystalline alumino-silicate carriers
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J21/00—Catalysts comprising the elements, oxides, or hydroxides of magnesium, boron, aluminium, carbon, silicon, titanium, zirconium, or hafnium
- B01J21/12—Silica and alumina
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/10—After treatment, characterised by the effect to be obtained
- B01J2229/20—After treatment, characterised by the effect to be obtained to introduce other elements in the catalyst composition comprising the molecular sieve, but not specially in or on the molecular sieve itself
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J2229/00—Aspects of molecular sieve catalysts not covered by B01J29/00
- B01J2229/30—After treatment, characterised by the means used
- B01J2229/42—Addition of matrix or binder particles
-
- B—PERFORMING OPERATIONS; TRANSPORTING
- B01—PHYSICAL OR CHEMICAL PROCESSES OR APPARATUS IN GENERAL
- B01J—CHEMICAL OR PHYSICAL PROCESSES, e.g. CATALYSIS OR COLLOID CHEMISTRY; THEIR RELEVANT APPARATUS
- B01J37/00—Processes, in general, for preparing catalysts; Processes, in general, for activation of catalysts
- B01J37/0009—Use of binding agents; Moulding; Pressing; Powdering; Granulating; Addition of materials ameliorating the mechanical properties of the product catalyst
Definitions
- the present invention relates to a method for hydrocracking wax.
- Patent Documents 1 to 3 describe hydrocracking methods using FT wax as a raw material.
- Patent Document 1 International Publication No. 2004/028688 Pamphlet
- Patent Document 2 Japanese Patent Application Laid-Open No. 2004-255241
- Patent Document 3 Japanese Patent Laid-Open No. 2004-255242
- diesel oil the properties required for diesel oil vary depending on the usage environment, and in JIS K 2204 (2004), such as No. 1 diesel oil, No. 1 diesel oil, No. 2 diesel oil, No. 3 diesel oil, and No. 3 diesel oil. It is classified. Among these, No. 3 diesel oil and special No. 3 diesel oil, which are specifications for cold regions, are required to have stricter properties than other diesel oils in terms of pour point and the like.
- the present invention has been made in view of such a situation, and when hydrocracking a raw material containing normal paraffin, it is possible to sufficiently reduce the pour point of the obtained decomposition product. It is an object of the present invention to provide a hydrocracking method useful for producing light oil for cold regions.
- the present inventors have determined that the conversion rate defined by the formula (1) is within a predetermined range using a wax having a high content of normal paraffin as a raw material. It was found that the above problems could be solved by hydrocracking the raw material wax so that the present invention was completed.
- the wax hydrocracking method of the present invention is defined by the following formula (1): a raw material wax containing 70% by mass or more of normal paraffins having 20 or more carbon atoms in the presence of a hydrocracking catalyst.
- the hydrocracking is characterized in that the conversion rate is 55 to 95% by mass.
- the mass of the wax fraction with a boiling point of 360 ° C or higher is the fraction of the wax fraction with a boiling point of 360 ° C or higher contained in the raw material wax.
- the mass of the fraction with a boiling point of less than 360 ° C indicates the total mass of the fraction with a boiling point of less than 360 ° C contained in the decomposition product obtained by hydrocracking.
- the hydrocracking method of the present invention when hydrocracking a raw material containing normal paraffin, it is possible to sufficiently reduce the pour point of the resulting cracked product. Therefore, the hydrocracking method of the present invention reduces the consumption of kerosene used when producing light oil for cold regions. It is very useful in that it can be reduced.
- the hydrocracking catalyst preferably contains USY zeolite and one or more solid acids selected from silica alumina, alumina polya and silica zirconia. Masle.
- the average particle size of USY zeolite is preferably 1.0 II m or less.
- FIG. 1 is an explanatory view showing an example of a fixed bed reactor used in the present invention.
- FIG. 1 is an explanatory view showing an example of a fixed bed reactor preferably used in the present invention.
- a hydrocracking catalyst layer 2 is provided in the reaction tower 1.
- a line L1 for supplying hydrogen into the reaction tower 1 is connected to the top of the reaction tower 1, and the raw material wax is supplied to the upstream side of the connection section with the reaction tower 1 in the line L1.
- Line L2 is connected.
- the bottom of the reaction tower 1 is connected to a line L3 for extracting the decomposition product after the hydrocracking from the reaction tower 1, and the other end of the line L3 is connected to the atmospheric pressure distillation apparatus 3. ing.
- the distillation apparatus 3 is capable of fractionating a light fraction having a boiling point of 260 to 360 ° C. produced by hydrocracking and other fractions.
- Other fractions include a naphtha fraction with a boiling point of less than 160 ° C, a kerosene fraction with a boiling point of 160-260 ° C, and a wax fraction with a boiling point of 360 ° C or higher.
- the fractions fractionated in the distillation apparatus 3 are transferred to subsequent processes by lines (L4 to L7) connected to the distillation apparatus 3, respectively.
- a petroleum or synthetic wax containing 70% by mass or more, more preferably 80% by mass or more of normal paraffin having 20 or more carbon atoms (preferably 20 to 100) is preferably used.
- wax include so-called FT wax produced by FT synthesis in a force synthesis system such as slack wax and microwax in petroleum. If the content of normal paraffins having 20 or more carbon atoms is less than 70% by mass, the pour point of the gas oil fraction obtained by hydrocracking this will be high, and it will not be possible to satisfy the No. 3 diesel oil standard. .
- the hydrocracking catalyst constituting the hydrocracking catalyst layer 2 is not particularly limited, but the hydrocracking catalyst is supported by ⁇ zeolite, mordenite, USY zeolite, SSZ-2 2, SAP ⁇ _ 11
- solid acids such as silica anolemina, anole minaboria, and silica zircoure can be used. Preferred
- the average particle size is 1.0.
- / i m or less is preferable 0.5 ⁇ or less is more preferable.
- the average particle size of USY zeolite exceeds 1.0 ⁇ , the pour point of the light oil fraction tends to increase.
- the molar ratio of silica / alumina in USY zeolite is preferably 25 to 80, more preferably 28 to 50.
- the silica / alumina molar ratio is less than 25, the yield of light oil fraction tends to decrease.
- the silica / alumina molar ratio exceeds 80, there is no problem in the yield of the light oil fraction, but the catalytic activity is lowered, so the reaction temperature needs to be increased and the catalyst life tends to be shortened .
- the content of USY zeolite is preferably 6% by mass or less, more preferably 4% by mass or less, and still more preferably 3% by mass or less, based on the total amount of the hydrocracking catalyst.
- the content of USY zeolite exceeds S6% by mass, the yield of light oil fraction tends to decrease.
- the hydrocracking catalyst may further contain a binder for forming a carrier.
- a binder for forming a carrier.
- the binder is not particularly limited, but preferred binders include alumina or silica, and alumina is preferred.
- the shape of the carrier is not particularly limited, and may be a granular shape, a cylindrical shape (pellet), or the like.
- hydrocracking catalyst a catalyst in which a metal of Group VIII of the periodic table is supported on the above support is preferable.
- the supported metal nickel and rhodium, palladium, iridium and platinum are preferable, and palladium and platinum are more preferable. These supported metals may be used alone or in combination of two or more.
- the hydrocracking catalyst constituting the hydrocracking catalyst layer 2 contains the above metal, it is preferable to reduce the metal in a reducing gas atmosphere such as hydrogen before hydrocracking.
- the reduction conditions are not particularly limited, but the reduction temperature is preferably 300 to 360 ° C., and the reduction time is preferably 1 to 6 hours.
- the conversion rate defined by the above formula (1) is 55 to 95% by mass (preferably 55 to 80% by mass). Thus, it is necessary to carry out hydrocracking. If the conversion rate is less than 55% by mass, the pour point of the gas oil fraction cannot meet the specifications of No. 3 gas oil. On the other hand, if the conversion rate exceeds 95% by mass, the standard of No. 3 diesel oil can be satisfied, but the yield decreases and the economics of the process deteriorates.
- the reaction conditions for the hydrocracking of the raw material wax are not particularly limited as long as the conversion rate defined by the above formula (1) is 55 to 95% by mass, but the reaction temperature Is preferably 370 ° C or lower. When the reaction temperature exceeds 370 ° C, aromatic compounds are likely to be formed, which is not preferable as a clean fuel substrate.
- the reaction pressure is not particularly limited, but the hydrogen partial pressure is preferably 1 to 12 MPa, more preferably 2 to 6 MPa.
- the liquid space velocity of the raw material wax is not particularly limited, but is preferably 0.2 to 5. Oh—, more preferably 0.5 to 3. Oh.
- the hydrogen Z oil ratio is not particularly limited. Preferably, it is 200 to 850 NL / L, and more preferably 350 to 650 NL /: L.
- the raw material wax containing 70% by mass or more of normal paraffins having 20 or more carbon atoms so that the conversion rate defined by the above formula (1) is 55 to 95% by mass is hydrocracked.
- a light oil fraction having a sufficiently low pour point can be obtained in a high yield. Since such a light oil fraction can meet the standards of No. 3 light oil specified in JIS, the light oil fraction can be used as a light oil base material. Therefore, it is possible to sufficiently reduce the consumption of kerosene used when producing light oil for cold regions.
- the present invention is not limited to the above embodiment.
- the hydrocracking catalyst layer 2 has a single layer structure, but different types of hydrocracking catalyst layers may be laminated to form a multilayer structure.
- the fixed bed reaction apparatus is exemplified as the apparatus for hydrocracking the raw material wax, but is not particularly limited as long as the raw material wax and the hydrocracking catalyst can be brought into contact with each other.
- a fluidized bed reactor may be used.
- the hydrocracking catalyst was subjected to reduction treatment at 345 ° C for 4 hours in a hydrogen stream. Thereafter, the raw material wax was hydrocracked.
- FT wax carbon number 21-80, normal paraffin 95% by mass
- hydrocracking reaction The conditions are as follows: The liquid space velocity of the raw material wax relative to the total amount of the hydrocracking catalyst is 2.0 h _ 1 (liquid flow rate of the raw material wax: 200 ml / h), the hydrogen partial pressure is 3 MPa, and the hydrogen / oil ratio is 570 NL / L.
- the reaction temperature was set so that the conversion rate defined by the above formula (1) was 60% by mass. The reaction temperature at this time was 293 ° C.
- the obtained decomposition product was distilled to obtain a gas oil fraction having a boiling point of 260 to 360 ° C.
- Table 1 shows the properties of the gas oil fraction obtained and the gas oil yield.
- the light oil yield is directly calculated by the following formula (2).
- Light oil yield (mass of gas oil fraction) / (mass of raw material wax) X 100 (2)
- Table 1 shows the characteristics of light oil fractions: flash point, 90% distillation temperature, pour point, clogging point, residual carbon content of 10% residual oil, cetane number, kinematic viscosity (30 ° C), Sulfur content and density (15 ° C) are shown.
- Table 1 also lists the standards for No. 3 diesel oil.
- the raw material wax was hydrocracked and the cracked product was distilled in the same manner as in Example 1 except that the reaction temperature was set so that the conversion rate defined by the above formula (1) was 82% by mass. A gas oil fraction was obtained. The reaction temperature at this time was 301 ° C. Table 1 shows the properties of the gas oil fraction obtained and the gas oil yield.
- the raw wax was hydrocracked and the cracked product was distilled in the same manner as in Example 1 except that 0.5 ⁇ m USY zeolite was used instead of 0.9 x m USY zeolite.
- a gas oil fraction was obtained.
- the reaction temperature at which the conversion rate was 60% by mass was 291 ° C.
- Table 1 shows the properties of the gas oil fraction obtained and the gas oil yield.
- the raw material wax was the same as in Example 1 except that 40 parts by mass of the FT wax used in Example 1 and 60 parts by mass of the petroleum-based paraffin wax were used as the raw material wax. Hydrolysis of tas and distillation of the decomposition products were performed to obtain a light oil fraction. The content of normal paraffins having 20 or more carbon atoms contained in the raw material nitrogen was 86% by mass. The reaction temperature at which the conversion was 60% by mass was 292 ° C. Table 1 shows the properties of the gas oil fraction obtained and the gas oil yield.
- the raw wax was hydrocracked and decomposed in the same manner as in Example 1 except that a petroleum paraffin wax having a normal paraffin content of 20 or more carbon atoms of 67% by mass was used as the raw wax.
- the gas oil fraction was obtained.
- the reaction temperature at which the conversion rate was 60% by mass was 298 ° C.
- Table 1 shows the properties of the gas oil fraction obtained and the gas oil yield.
- the raw wax was hydrocracked and the cracked product was distilled in the same manner as in Example 1 except that the reaction temperature was set so that the conversion rate defined by the above formula (1) was 40% by mass. A gas oil fraction was obtained. The reaction temperature at this time was 286 ° C. Table 1 shows the properties of the gas oil fraction obtained and the gas oil yield.
- Residual carbon content 0.01 0.01 0.01 0.01 0.02 0.02 0.02 or less
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- Chemical & Material Sciences (AREA)
- Crystallography & Structural Chemistry (AREA)
- Engineering & Computer Science (AREA)
- Chemical Kinetics & Catalysis (AREA)
- Oil, Petroleum & Natural Gas (AREA)
- Organic Chemistry (AREA)
- Inorganic Chemistry (AREA)
- General Chemical & Material Sciences (AREA)
- Materials Engineering (AREA)
- Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
- Catalysts (AREA)
Description
Claims
Priority Applications (1)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
AU2007231960A AU2007231960A1 (en) | 2006-03-30 | 2007-03-13 | Method of wax hydrocracking |
Applications Claiming Priority (2)
Application Number | Priority Date | Filing Date | Title |
---|---|---|---|
JP2006095181A JP2007269897A (ja) | 2006-03-30 | 2006-03-30 | ワックスの水素化分解方法 |
JP2006-095181 | 2006-03-30 |
Publications (1)
Publication Number | Publication Date |
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WO2007114001A1 true WO2007114001A1 (ja) | 2007-10-11 |
Family
ID=38563273
Family Applications (1)
Application Number | Title | Priority Date | Filing Date |
---|---|---|---|
PCT/JP2007/054926 WO2007114001A1 (ja) | 2006-03-30 | 2007-03-13 | ワックスの水素化分解方法 |
Country Status (5)
Country | Link |
---|---|
JP (1) | JP2007269897A (ja) |
CN (1) | CN101400767A (ja) |
AU (1) | AU2007231960A1 (ja) |
RU (1) | RU2008142990A (ja) |
WO (1) | WO2007114001A1 (ja) |
Families Citing this family (1)
Publication number | Priority date | Publication date | Assignee | Title |
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JP5737981B2 (ja) | 2011-02-04 | 2015-06-17 | 独立行政法人石油天然ガス・金属鉱物資源機構 | 炭化水素油の製造方法 |
Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01308492A (ja) * | 1987-12-18 | 1989-12-13 | Exxon Res & Eng Co | 中間留出物製品を生成するためのろうの水素異性化方法 |
JPH05302088A (ja) * | 1991-09-12 | 1993-11-16 | Shell Internatl Res Maatschappij Bv | 炭化水素燃料の製造方法 |
JP2001522382A (ja) * | 1997-02-07 | 2001-11-13 | エクソン リサーチ アンド エンジニアリング カンパニー | セタン価、潤滑性、および安定性を向上させるためのディーゼル添加剤 |
WO2004028688A1 (ja) * | 2002-09-24 | 2004-04-08 | Nippon Oil Corporation | 水素化分解触媒および液状炭化水素の製造方法 |
JP2005279382A (ja) * | 2004-03-29 | 2005-10-13 | Nippon Oil Corp | 水素化分解触媒および液状炭化水素の製造方法 |
Family Cites Families (2)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
WO2001090280A2 (en) * | 2000-05-25 | 2001-11-29 | Sasol Technology (Pty) Ltd | A hydrocracking catalyst and a diesel production process |
JP4047206B2 (ja) * | 2003-03-20 | 2008-02-13 | 株式会社ジャパンエナジー | 環境対応軽油およびその製造方法 |
-
2006
- 2006-03-30 JP JP2006095181A patent/JP2007269897A/ja active Pending
-
2007
- 2007-03-13 AU AU2007231960A patent/AU2007231960A1/en not_active Abandoned
- 2007-03-13 WO PCT/JP2007/054926 patent/WO2007114001A1/ja active Application Filing
- 2007-03-13 RU RU2008142990/04A patent/RU2008142990A/ru not_active Application Discontinuation
- 2007-03-13 CN CNA200780008560XA patent/CN101400767A/zh active Pending
Patent Citations (5)
Publication number | Priority date | Publication date | Assignee | Title |
---|---|---|---|---|
JPH01308492A (ja) * | 1987-12-18 | 1989-12-13 | Exxon Res & Eng Co | 中間留出物製品を生成するためのろうの水素異性化方法 |
JPH05302088A (ja) * | 1991-09-12 | 1993-11-16 | Shell Internatl Res Maatschappij Bv | 炭化水素燃料の製造方法 |
JP2001522382A (ja) * | 1997-02-07 | 2001-11-13 | エクソン リサーチ アンド エンジニアリング カンパニー | セタン価、潤滑性、および安定性を向上させるためのディーゼル添加剤 |
WO2004028688A1 (ja) * | 2002-09-24 | 2004-04-08 | Nippon Oil Corporation | 水素化分解触媒および液状炭化水素の製造方法 |
JP2005279382A (ja) * | 2004-03-29 | 2005-10-13 | Nippon Oil Corp | 水素化分解触媒および液状炭化水素の製造方法 |
Also Published As
Publication number | Publication date |
---|---|
AU2007231960A1 (en) | 2007-10-11 |
CN101400767A (zh) | 2009-04-01 |
RU2008142990A (ru) | 2010-05-10 |
JP2007269897A (ja) | 2007-10-18 |
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