US20090159490A1 - Method of hydrogenolysis of wax and process for producing fuel base - Google Patents

Method of hydrogenolysis of wax and process for producing fuel base Download PDF

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US20090159490A1
US20090159490A1 US12/161,998 US16199807A US2009159490A1 US 20090159490 A1 US20090159490 A1 US 20090159490A1 US 16199807 A US16199807 A US 16199807A US 2009159490 A1 US2009159490 A1 US 2009159490A1
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hydrocracking
wax
fraction
untreated
heart
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Hiroyuki Seki
Masahiro Higashi
Minoru Hatayama
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Eneos Corp
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    • 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
    • B01J29/084—Y-type faujasite
    • 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
    • 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
    • B01J35/00—Catalysts, in general, characterised by their form or physical properties
    • B01J35/40—Catalysts, in general, characterised by their form or physical properties characterised by dimensions, e.g. grain size
    • 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
    • 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
    • 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
    • C10G47/18—Crystalline alumino-silicate carriers the catalyst containing platinum group metals or compounds thereof
    • 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
    • B01J21/02—Boron or aluminium; Oxides or hydroxides thereof
    • 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
    • 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
    • C—CHEMISTRY; METALLURGY
    • C10—PETROLEUM, GAS OR COKE INDUSTRIES; TECHNICAL GASES CONTAINING CARBON MONOXIDE; FUELS; LUBRICANTS; PEAT
    • C10G—CRACKING HYDROCARBON OILS; PRODUCTION OF LIQUID HYDROCARBON MIXTURES, e.g. BY DESTRUCTIVE HYDROGENATION, OLIGOMERISATION, POLYMERISATION; RECOVERY OF HYDROCARBON OILS FROM OIL-SHALE, OIL-SAND, OR GASES; REFINING MIXTURES MAINLY CONSISTING OF HYDROCARBONS; REFORMING OF NAPHTHA; MINERAL WAXES
    • C10G2300/00—Aspects relating to hydrocarbon processing covered by groups C10G1/00 - C10G99/00
    • C10G2300/40—Characteristics of the process deviating from typical ways of processing
    • C10G2300/4081—Recycling aspects

Definitions

  • the present invention relates to a hydrocracking method of wax and to a production method of a fuel base material.
  • FT Fischer-Tropsch
  • FT waxes can also be converted to heart-cut fractions (fuel bases such as kerosene and light oil) by hydrocracking.
  • Patent documents 1-3 disclose hydrocracking processes using FT waxes as starting materials.
  • Patent document 1 International Patent Publication No. 2004/028688
  • Patent document 2 Japanese Unexamined Patent Publication No. 2004-255241
  • Patent document 3 Japanese Unexamined Patent Publication No. 2004-255242
  • Hydrocracking of wax usually leaves an untreated wax fraction.
  • the reuse of an untreated wax fraction as the starting material for hydrocracking will henceforth be referred to as “bottom recycling”, for convenience.
  • the normal paraffin content is preferably low while the isoparaffin content is preferably high.
  • a high normal paraffin content results in an insufficient octane number.
  • a high normal paraffin content impairs the low-temperature flow properties, often restricting its use as a commercial product.
  • the normal paraffin content of heart-cut fractions obtained under such reaction conditions tends to be higher.
  • the normal paraffin content of the obtained heart-cut fraction can be reduced by employing more severe reaction conditions for hydrocracking, although this tends to promote overcracking of the produced heart-cut fraction and result in a reduced heart-cut fraction yield.
  • the hydrocracking method of wax of the invention is a hydrocracking process wherein crude wax is subjected to hydrocracking and the untreated wax fraction that is produced after the hydrocracking is re-supplied for hydrocracking, and wherein hydrocracking of the crude wax and untreated wax fraction is carried out in the presence of a hydrocracking catalyst in such a manner that the conversion ratio is 50-85% by mass from the wax fraction with a boiling point of 360° C. or above to the light fraction with a boiling point of below 360° C.
  • the production method of a fuel base material according to the invention comprises a hydrocracking step wherein crude wax is subjected to hydrocracking and the untreated wax fraction that is produced after the hydrocracking is re-supplied for hydrocracking, in which hydrocracking step hydrocracking of the crude wax and untreated wax fraction is carried out in the presence of a hydrocracking catalyst in such a manner that the conversion ratio is 50-85% by mass from the wax fraction with a boiling point of 360° C. or above to the light fraction with a boiling point of below 360° C.
  • the conversion ratio from the wax fraction with a boiling point of 360° C. or above to the light fraction with a boiling point of below 360° C. is the conversion ratio as defined by formula (1) below.
  • “weight of wax fraction with boiling point of 360° C. and above” means the total weight of wax fractions with boiling points of 360° C. and above in the crude wax and untreated wax fraction, while “weight of fraction with boiling point of below 360° C.” means the weight of the fraction with a boiling point of below 360° C. in the treated product obtained by the hydrocracking.
  • the hydrocracking catalyst preferably contains USY-zeolite and at least one solid acid selected from among silica-alumina, alumina-boria and silica-zirconia.
  • the mean particle size of the USY-zeolite is preferably no greater than 1.0 ⁇ m.
  • the USY-zeolite content is also preferably no greater than 6% by mass based on the total weight of the hydrocracking catalyst.
  • the reaction temperature for the crude wax and untreated wax fraction during the hydrocracking is preferably no greater than 370° C.
  • the hydrocracking method of wax and fuel base manufacturing process of the invention can achieve both an increased heart-cut fraction yield (as the target product of the hydrocracking) and a reduced normal paraffin content in the heart-cut fraction, during bottom recycling of the untreated wax.
  • FIG. 1 is an illustration showing an example of a fixed bed reactor used for the invention.
  • FIG. 1 is an illustration showing an example of a fixed bed reactor suitable for use according to the invention.
  • a hydrocracking catalyst layer 2 is provided in a reaction column 1 .
  • a line L 1 for supply of hydrogen into the reaction column 1
  • a line L 2 for supply of the crude wax is connected upstream from the connection of the line L 1 with the reaction column 1 .
  • a line L 3 for removal of the hydrocracked decomposition product oil from the reaction column 1
  • the other end of the line L 3 is connected to the distilling apparatus 3 .
  • the distilling apparatus 3 is capable of fractionating the light fraction with a boiling point of below 360° C.
  • the crude wax used is preferably a petroleum-based or synthetic wax comprising at least 70% by mass of C 16 or greater and preferably C 20 or greater normal paraffins.
  • waxes there may be mentioned petroleum-based waxes such as slack wax and microwax, or synthetic waxes such as “FT wax” produced by FT synthesis.
  • the hydrocracking catalyst is preferably one comprising one or more selected from among USY-zeolite, silica-alumina, silica-zirconia, alumina-boria and silicoaluminophosphates (SAPO-11 or the like) as the carrier, more preferably one comprising USY-zeolite and one or more amorphous solid acids selected from among silica-alumina, alumina-boria and silica-zirconia, and most preferably one comprising USY-zeolite and alumina-boria.
  • SAPO-11 silicoaluminophosphates
  • the mean particle size is preferably no greater than 1.0 ⁇ m and even more preferably no greater than 0.5 ⁇ m. If the mean particle size of the USY-zeolite exceeds 1.0 ⁇ m, the heart-cut fraction (the target product of the hydrocracking) will be lighter and its yield will tend to be reduced.
  • the molar ratio of silica/alumina in the USY-zeolite is preferably 25-80 and more preferably 28-50.
  • a silica/alumina molar ratio of less than 25 will tend to lower the selectivity of the heart-cut fraction.
  • a silica/alumina molar ratio of greater than 80 will not impair the selectivity of the heart-cut fraction, the reaction temperature must be increased due to the lower catalytic activity, and therefore the catalyst life tends to be shorter.
  • the USY-zeolite content is preferably no greater than 6% by mass, more preferably no greater than 4% by mass and even more preferably no greater than 3% by mass based on the total weight of the hydrocracking catalyst.
  • a USY-zeolite content of greater than 6% by mass will tend to lower the selectivity of the heart-cut fraction.
  • the hydrocracking catalyst may further contain a binder for molding of the carrier.
  • a binder for molding of the carrier.
  • binders include alumina and silica, with alumina being especially preferred.
  • the shape of the carrier is also not particularly restricted, and it may be in a form of particles, cylinders (pellets) or the like.
  • the hydrocracking catalyst preferably comprises a metal belonging to Group VIII of the Periodic Table supported on the aforementioned carrier.
  • the supported metal is preferably nickel, rhodium, palladium, iridium or platinum, with palladium and platinum being preferred. Such metals may be supported alone or in combinations of two or more.
  • the metal is preferably reduced in a reducing gas atmosphere such as hydrogen prior to hydrocracking.
  • a reducing gas atmosphere such as hydrogen prior to hydrocracking.
  • the reducing conditions are not particularly restricted, but preferably the reducing temperature is 300-360° C. and the reducing time is 1-6 hours.
  • the reaction conditions are preferably selected so that the conversion ratio as defined by formula (1) above is 50-85% by mass, with the hydrocracking preferably being conducted for a prescribed time to stabilize the catalytic activity of the hydrocracking catalyst layer 2 .
  • the cracked oil produced by hydrocracking using the crude wax alone is transported from the reaction column 1 to the distilling apparatus 3 , for fractionation of the untreated wax fraction with a boiling point of 360° C. and above and the light fraction with a boiling point of below 360° C.
  • the untreated wax fraction with a boiling point of 360° C. and above is then introduced through the top of the reaction column 1 together with the crude wax, for hydrocracking of the mixture of the crude wax and untreated wax fraction.
  • the hydrocracking In order to simultaneously achieve an increased yield of heart-cut fraction as the target product of the hydrocracking and a reduced normal paraffin content in the heart-cut fraction, the hydrocracking must be conducted in such a manner that the conversion ratio as defined by formula (1) above is 50-85% by mass and more preferably 60-78% by mass. If the conversion ratio is less than 50% by mass, isomerization of normal paraffins to isoparaffins will not proceed sufficiently, such that the normal paraffin content of the obtained heart-cut fraction will not be adequately reduced. If the conversion ratio exceeds 85% by mass, the heart-cut fraction yield will be reduced as a result of overcracking.
  • the mixing ratio of the crude wax and untreated wax fraction is not particularly restricted so long as the conversion ratio as defined by formula (1) above is 50-85% by mass, but the untreated wax fraction content is preferably 10-60% by mass and more preferably 15-50% by mass based on the total of the crude wax and untreated wax fraction.
  • the reaction conditions for hydrocracking of the mixture of the crude wax and untreated wax fraction are also not particularly restricted so long as the conversion ratio as defined by formula (1) above is 50-85% by mass, but preferably the reaction temperature is not above 370° C. A reaction temperature exceeding 370° C. is not preferred for a clean fuel base because aromatic compounds will tend to be produced.
  • the reaction pressure is also not particularly restricted, but the hydrogen partial pressure is preferably 1-12 MPa and more preferably 2-6 MPa.
  • the liquid space velocity of the mixture of the crude wax and the unreacted wax fraction is not particularly restricted but is preferably 0.2-5.0 h ⁇ 1 and more preferably 0.5-3.0 h ⁇ 1 .
  • a liquid space velocity of smaller than 0.2 h ⁇ 1 will lead to problems such as requirement for an excessively large reaction column, reduced selectivity of the heart-cut fraction and inadequate isomerization.
  • a liquid space velocity of greater than 5.0 h ⁇ 1 will require a higher reaction temperature because of low activity, and the catalyst life will thus be shortened.
  • the hydrogen/oil ratio is not particularly restricted but is preferably 200-850 NL/L and more preferably 350-650 NL/L.
  • the mode of the invention explained here accomplishes hydrocracking of a mixture of crude wax and untreated wax in such a manner that the conversion ratio as defined by formula (1) above is 50-85% by mass, thereby making it possible to simultaneously achieve an increased heart-cut fraction yield (as the target product of the hydrocracking) and a reduced normal paraffin content in the heart-cut fraction.
  • the invention is not limited to this mode, however.
  • the untreated wax fraction and crude wax are introduced as a mixture into the reaction column 1 according to this mode, the untreated wax fraction and crude wax may instead be introduced separately into the reaction column 1 .
  • the untreated wax fraction may instead be introduced from the side of the reaction column 1 .
  • the position where the line L 4 is connected to the reaction column 1 is preferably upstream from the upstream end of the hydrocracking catalyst layer 2 .
  • hydrocracking catalyst layer 2 has a single-layer structure according to this mode, different hydrocracking catalyst layers may be laminated to form a multilayer structure instead.
  • a platinic chloride aqueous solution was impregnated into the carrier, for loading of platinum to 0.6% by mass with respect to the carrier. This was dried and fired to obtain a hydrocracking catalyst.
  • the hydrocracking catalyst was subjected to reduction treatment at 345° C. for 4 hours under a hydrogen stream, and then the crude wax alone was subjected to hydrocracking.
  • FT wax C21-80, normal paraffin content: 95% by mass
  • the liquid space velocity of the crude wax was 2.0 h ⁇ 1 (crude wax liquid flow rate: 600 ml/h) with respect to the total amount of hydrocracking catalyst
  • the hydrogen partial pressure was 3 MPa and the hydrogen/oil ratio was 570 NL/L
  • the reaction temperature was set for a conversion ratio of 55% by mass as defined by formula (1).
  • the reaction temperature was set to 292° C.
  • the untreated wax fraction with a boiling point of 360° C. and above was transported to the line L 4 , the untreated wax fraction and crude wax were combined to an untreated wax content of 45% by mass based on the total weight of the untreated wax fraction and crude wax, and this mixture was used as the starting material for hydrocracking.
  • the reaction temperature, set for a conversion ratio of 55% by mass as defined by formula (1) above, was 290° C.
  • the other reaction conditions were the same as for hydrocracking of FT wax alone.
  • heart-cut fraction selectivity the proportion of the heart-cut fraction with a boiling point of between 145° C. and 360° C. in the light fraction with a boiling point of below 360° C.
  • a bottom recycling experiment was conducted in the same manner as Example 1, except that the conversion ratio represented by formula (1) above was 75% by mass for the hydrocracking of crude wax alone, the conversion ratio represented by general formula (1) for hydrocracking of the crude wax and untreated wax fraction was 75% by mass, and the untreated wax content of the mixture was 25% by mass.
  • the reaction temperature for hydrocracking of the mixture of the crude wax and untreated wax fraction was 299° C.
  • the heart-cut fraction selectivity obtained by chromatographic analysis of the treated product oil and the normal paraffin and aromatic compound contents of the heart-cut fraction are listed in Table 1.
  • a hydrocracking catalyst was prepared in the same manner as Example 1, except that USY-zeolite with a mean particle size of 0.42 ⁇ m (silica/alumina molar ratio: 37) was used instead of the USY-zeolite with a mean particle size of 0.82 ⁇ m.
  • a bottom recycling experiment was then conducted in the same manner as Example 1, except for using this hydrocracking catalyst.
  • the reaction temperature for hydrocracking of the crude wax and untreated wax fraction was 296° C.
  • the heart-cut fraction selectivity obtained by chromatographic analysis of the treated product oil and the normal paraffin and aromatic compound contents of the heart-cut fraction are listed in Table 1.
  • a hydrocracking catalyst was prepared in the same manner as Example 1, except that the USY-zeolite content was changed from 4% by mass to 2% by mass.
  • a bottom recycling experiment was then conducted in the same manner as Example 1, except for using this hydrocracking catalyst.
  • the reaction temperature for hydrocracking of the crude wax and untreated wax fraction was 318° C.
  • the heart-cut fraction selectivity obtained by chromatographic analysis of the treated product oil and the normal paraffin and aromatic compound contents of the heart-cut fraction are listed in Table 1.
  • Example 2 A bottom recycling experiment was conducted in the same manner as Example 1, except that the wax used (normal paraffin content: 76% by mass) was a mixture of FT wax as the crude wax and a petroleum-based paraffin wax in a weight ratio of 60:40.
  • the reaction temperature for hydrocracking of the crude wax and untreated wax fraction was 326° C.
  • the heart-cut fraction selectivity obtained by chromatographic analysis of the treated product oil and the normal paraffin and aromatic compound contents of the heart-cut fraction are listed in Table 1.
  • a bottom recycling experiment was conducted in the same manner as Example 1, except that the untreated wax was not mixed with the crude FT wax, and the position of connection of the reaction column line 1 with the line L 4 was switched to a position at the side of the reaction column 1 at 3 L/5 from the upstream end of the hydrocracking catalyst layer 2 (where L represents the distance from the upstream end to the downstream end of the hydrocracking catalyst layer 2 ).
  • the reaction temperature for hydrocracking of the crude wax and untreated wax fraction was 292° C.
  • the heart-cut fraction selectivity obtained by chromatographic analysis of the treated product oil and the normal paraffin and aromatic compound contents of the heart-cut fraction are listed in Table 1.
  • a bottom recycling experiment was conducted in the same manner as Example 1, except that the conversion ratio represented by formula (1) above was 40% by mass for the hydrocracking of crude wax alone, the conversion ratio represented by general formula (1) for hydrocracking of the crude wax and untreated wax fraction was 60% by mass, and the untreated wax content of the mixture was 40% by mass.
  • the reaction temperature for hydrocracking of the mixture of the crude wax and untreated wax fraction was 274° C.
  • the heart-cut fraction selectivity obtained by chromatographic analysis of the treated product oil and the normal paraffin and aromatic compound contents of the heart-cut fraction are listed in Table 1.
  • Hydrocracking of wax was carried out in the same manner as Example 1, except that the conversion ratio represented by formula (1) above was 95% by mass for the hydrocracking of crude wax alone, the conversion ratio represented by general formula (1) for hydrocracking of the crude wax and untreated wax fraction was 95% by mass, and the untreated wax content of the mixture was 5% by mass.
  • the reaction temperature for hydrocracking of the mixture of the crude wax and untreated wax fraction was 312° C.
  • the heart-cut fraction selectivity obtained by chromatographic analysis of the treated product oil and the normal paraffin and aromatic compound contents of the heart-cut fraction are listed in Table 1.
  • Examples 1-6 had high heart-cut fraction selectivity and low normal paraffin contents in the heart-cut fraction, thus demonstrating that it is possible to simultaneously achieve increased heart-cut fraction yield and reduced normal paraffin content in the heart-cut fraction. Furthermore, no aromatic compounds were detected in the heart-cut fraction in Examples 1-6.
  • the hydrocracking method of wax and fuel base manufacturing process of the invention can simultaneously achieve both an increased heart-cut fraction yield (as the target product of the hydrocracking) and a reduced normal paraffin content in the heart-cut fraction, when untreated wax is subjected to bottom recycling, and is thus useful for producing of environmentally-friendly, clean liquid fuel.

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  • Chemical & Material Sciences (AREA)
  • Engineering & Computer Science (AREA)
  • Organic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Oil, Petroleum & Natural Gas (AREA)
  • Crystallography & Structural Chemistry (AREA)
  • Materials Engineering (AREA)
  • Inorganic Chemistry (AREA)
  • General Chemical & Material Sciences (AREA)
  • Production Of Liquid Hydrocarbon Mixture For Refining Petroleum (AREA)
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US12/161,998 2006-01-30 2007-01-18 Method of hydrogenolysis of wax and process for producing fuel base Abandoned US20090159490A1 (en)

Applications Claiming Priority (3)

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JP2006021291A JP5349736B2 (ja) 2006-01-30 2006-01-30 ワックスの水素化分解方法
JP2006-021291 2006-01-30
PCT/JP2007/050658 WO2007086299A1 (ja) 2006-01-30 2007-01-18 ワックスの水素化分解方法及び燃料基材の製造方法

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US (1) US20090159490A1 (ja)
EP (1) EP1953208A4 (ja)
JP (1) JP5349736B2 (ja)
CN (1) CN101356253A (ja)
AU (1) AU2007208855B2 (ja)
MY (1) MY150760A (ja)
WO (1) WO2007086299A1 (ja)

Cited By (3)

* Cited by examiner, † Cited by third party
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EP1953208A1 (en) 2008-08-06
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AU2007208855A1 (en) 2007-08-02
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AU2007208855B2 (en) 2011-09-22

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