JP6181538B2 - FUEL OIL BASE, PROCESS FOR PRODUCING THE SAME, AND FUEL OIL COMPOSITION - Google Patents

Description

  The present invention relates to a fuel oil base material using biomass as a raw material, a method for producing the same, and a fuel oil composition containing the fuel oil base material.

  2. Description of the Related Art Conventionally, the use of biological resources (so-called biomass) including plant resources as raw materials for gasoline, kerosene, and light oil has been promoted. In particular, biomass fuel derived from plant resources is an organic compound converted from carbon atoms of carbon dioxide taken from the atmosphere by photosynthesis during plant growth, so the biomass fuel derived from plant resources is burned and discharged Carbon dioxide does not lead to an increase in the total amount of carbon dioxide in the atmosphere. Thus, the biomass fuel derived from plant resources is beneficial from the viewpoint of carbon neutrality.

Fatty Acid Methyl Ester (hereinafter referred to as FAME) FAME, which is an example of biomass fuel, is a transesterification reaction between methanol and animal and vegetable fats and oils having a triglyceride structure in which glycerin and a fatty acid are ester-bonded. Is obtained.
However, practical problems have been pointed out in FAME. For example, FAME has a double bond. Double bonds affect oxidative stability and low temperature fluidity. When the amount of double bonds is large, the oxidation stability is lowered, and when the amount of double bonds is small, low-temperature fluidity is deteriorated. For this reason, it is difficult to adjust the double bond amount so as to achieve both the oxidation stability and the low temperature fluidity.
Moreover, since FAME has many heavier components than general diesel fuel, there was a concern that the burn-out property was poor, and fuel consumption deteriorated and unburned hydrocarbon emissions increased during combustion. Furthermore, since FAME is an oxygen-containing compound, there are concerns that it may deteriorate members such as metal and rubber used in the combustion engine, or increase emission of aldehydes during combustion.
As biomass fuel, hydro-treated biodiesel (HBD) obtained by deoxygenating, isomerizing, and hydrotreating animal and vegetable oils and fats having a triglyceride structure in addition to FAME has been proposed. Yes.
HBD also points out several problems. For example, since HBD has a density lower than that of general diesel fuel, fuel consumption is poor and lubricity is also poor. In addition, since isomerization is required to ensure fluidity at low temperatures, it is difficult to achieve complete carbon neutral when viewed over the entire life cycle.
Thus, there are many problems in the spread of biomass fuels such as FAME and HBD. However, if the ratio at which biomass fuel can be used as a raw material for current fuel oil increases, it will be even more beneficial for reducing carbon dioxide emissions. Thus, in recent years, some of the above-described problems have been improved (see Patent Documents 1 to 5).
However, in order to obtain a biomass fuel that satisfies various performances such as low temperature performance and high calorific value required for current fuel oil, many problems still remain, and further improvement is desired.

JP 2007-153928 A JP 2007-308565 A JP 2007-308566 A JP 2007-308567 A JP 2009-161669 A

  An object of this invention is to provide the fuel oil base material which is excellent in low-temperature performance, and can obtain the high calorific value, its manufacturing method, and the fuel oil composition containing this fuel oil base material.

  As a result of intensive studies, the present inventors have obtained a fuel oil base material obtained by deoxidizing and hydrocracking an oil extracted from biomass having a specific compound, which has excellent low-temperature performance and high calorific value. Based on this finding, the present invention has been completed.

That is, the present invention
[1] A saturated hydrocarbon containing 99% by volume or more based on a fuel oil base material, and at least one hydrocarbon compound selected from isoparaffin having 10 to 14 carbon atoms and naphthene having 10 to 14 carbon atoms based on the saturated hydrocarbon basis A fuel oil base containing 60% by volume or more,
[2] The fuel according to [1], wherein at least one hydrocarbon compound selected from the C10-14 isoparaffin and the C10-14 naphthene is contained in an amount of 90% by volume or more based on the saturated hydrocarbon. Oil base,
[3] The fuel oil according to the above [1] or [2], wherein the sulfur content is 1 mass ppm or less, the aromatic content is 0.1 vol% or less, the smoke point is 38 mm or more, and the precipitation point is −50 ° C. or less. Base material,
[4] A fuel oil composition comprising the fuel oil base material according to any one of [1] to [3] in an amount of 50% by volume to 100% by volume based on the fuel oil composition,
[5] The fuel oil composition according to the above [4], wherein the refractive index is 1.42 or more and 1.44 or less,
[6] A method for producing a fuel oil base material according to [1] to [4], wherein the oil component extracted from cashew nut shells is deoxygenated and hydrocracked.

  ADVANTAGE OF THE INVENTION According to this invention, the fuel oil base material which is excellent in low-temperature characteristics and can obtain high calorific value, the manufacturing method of this fuel oil base material, and the fuel oil composition containing this fuel oil base material can be provided.

[Fuel oil base material]
The fuel oil base material according to the embodiment of the present invention contains 99% by volume or more of saturated hydrocarbons based on the fuel oil base material, and is at least one selected from isoparaffin having 10 to 14 carbon atoms and naphthene having 10 to 14 carbon atoms. A hydrocarbon compound is contained in an amount of 60% by volume or more based on the saturated hydrocarbon.
Further, from the viewpoint of obtaining a high calorific value, in the fuel oil base material according to the present embodiment, at least one hydrocarbon compound selected from C10-14 isoparaffin and C10-14 naphthene is saturated carbonization. It is preferably contained in an amount of 90% by volume or more based on hydrogen.
The density at 15 ° C. of the fuel oil base material in the present embodiment is preferably 0.75 g / cm ³ or more and 0.87 g / cm ³ or less. More preferably, 0.760 g / cm ³ or more 0.84 g / cm ³ or less, more preferably, not more than 0.765 g / cm ³ or more 0.80 g / cm ^3, most preferably 0.775 g / cm ³ or more and 0.785 g / cm ³ or less. When the density at 15 ° C. is in the above range, the calorific value can be increased, and the low temperature performance and combustibility can be improved.

Moreover, it is preferable that the sulfur content of the fuel oil base material which concerns on this embodiment is 1 mass ppm or less.
The aromatic content is preferably 0.1% by volume or less.
The smoke point is preferably 38 mm or more.
The precipitation point is preferably −50 ° C. or lower.
The refractive index is preferably 1.42 or more and 1.44 or less. When the refractive index is within this range, a high calorific value can be maintained and the low-temperature performance can be kept good. From this viewpoint, the refractive index is more preferably 1.422 or more and 1.436 or less, and further preferably 1.424 or more and 1.432 or less.
The distillation characteristics of the fuel oil base material have a boiling range of 140 ° C. or more and 300 ° C. or less, a 10% by volume distillation temperature of 205 ° C. or less, and a 95% distillation temperature of 268 ° C. or less. Those having an end point of 300 ° C. or lower are preferred.
In this embodiment, the density at 15 ° C. is a density measured according to JIS K 2249 “Crude oil and petroleum product density test method and density / mass / capacity conversion table”.
The sulfur content is a value measured according to JIS K2541-6 ultraviolet fluorescence method.
The precipitation point is a value measured according to JIS K 2276 “Precipitation point test method (aviation fuel oil)”.
The smoke point is a value measured according to JIS K2537.
The flash point is a value measured according to JIS K 2265 1 (tag sealing type) below 60 ° C., and above 60 ° C. according to JIS K 2265 3 “How to find the flash point—Part 3: Pensky It is a value measured by the “Marten sealing method”.
The distillation property is measured according to a distillation test: JIS K 2254 (fuel oil distillation test method).
The aromatic content is a value measured according to JIS K 2536 “Fuel oil hydrocarbon component test method (fluorescent indicator adsorption method)”.
The calorific value is a value measured or calculated according to the estimation formula (clause number 6.3e) 1) of JIS K 2279 “Crude oil and petroleum products—heating value test method and calculation estimation method”.
The refractive index is a value measured according to JIS K 0062.
Identification and quantification of C10-14 isoparaffins and naphthenes were identified using the 7890A GC System (Agilent Technologies).

[Method for producing fuel oil base]
The method for producing a fuel oil base material according to the present embodiment uses a fuel oil extracted from a cashew nut shell (referred to as cashew nut shell oil) as a raw material oil, and this raw material oil is subjected to deoxygenation and hydrocracking treatment. A base material is manufactured.
Cashew nut shell oil includes at least one compound selected from anacardic acid, cardol, and cardanol. It is preferable that cashew nut shell oil decomposes anacardic acid by performing a heat treatment in advance. The heat-treated cashew nut shell oil contains 0% by mass or more and 10.0% by mass or less of anacardic acid, 0% by mass or more and 25.0% by mass or less of cardol, and cardanol 65.0% with respect to the total mass of cashew nut shell oil. It is preferable that the content is from 100% by mass to 100% by mass.
Further, the fuel of the present invention is not limited to cashew nut shell oil, and any biomass containing 40% by mass or more of an alkylbenzene compound having an alkyl group having 15 or more carbon atoms bonded thereto or a phenol compound having an alkyl group having 15 or more carbon atoms bonded thereto. It is advantageous to obtain an oil base.

<Deoxygenation and hydrocracking treatment>
Various methods can be selected as the deoxygenation and hydrocracking treatment methods. In the present embodiment, it is preferable to use a catalyst in consideration of the convenience of the treatment method and the selectivity of the product.
As the catalyst used for the deoxygenation treatment, a catalyst in which at least one of the metals in Groups 6, 8, 9, and 10 of the periodic table is supported on a refractory inorganic oxide carrier is preferable.
Examples of the refractory oxide carrier include alumina, silica, silica alumina, titania, magnesia, zinc oxide, crystalline aluminosilicate, clay mineral, or a mixture thereof. Among these, alumina, particularly γ-alumina is preferable. The average pores are preferably in the range of 50 to 150 mm, more preferably in the range of 60 to 140 mm. The shape may be a powder or a molded body such as a cylinder, a three-leaf, or a four-leaf.
The active component of Group 6 of the periodic table is preferably molybdenum or tungsten. Molybdenum compounds supporting these active ingredients on a carrier are preferably molybdenum trioxide, ammonium molybdate and the like, and tungsten compounds are preferably tungsten trioxide, ammonium tungstate and the like.
Examples of the active ingredients of Groups 8, 9, and 10 of the periodic table include iron, cobalt, nickel and the like. Of these, cobalt and nickel are preferred. Effective cobalt compounds for supporting these active ingredients on a carrier are preferably cobalt carbonate, basic cobalt carbonate, cobalt nitrate, and the like, and nickel compounds are preferably nickel carbonate, basic nickel carbonate, nickel nitrate, and the like.
Furthermore, a phosphorus compound can be supported, and as this phosphorus compound, various phosphoric acids such as phosphorus pentoxide and orthophosphoric acid are preferable.

The supported amount is 10 to 40% by mass of at least one of molybdenum and tungsten, 1 to 10% by mass of at least one of cobalt and nickel, and 1 to 10% by mass of phosphorus on the basis of oxide as a catalyst body. It is preferable that
Among these, at least one of molybdenum, cobalt, and nickel, particularly a combination of molybdenum and nickel or molybdenum and cobalt is preferable.
As the catalyst used for the hydrocracking treatment, at least one of the metals in Groups 6, 8, 9, and 10 of the periodic table was supported on a refractory inorganic oxide support containing crystalline aluminosilicate. A catalyst is preferred. The content of the crystalline aluminosilicate is preferably 5% by mass or more and 80% by mass or less in the refractory inorganic oxide support.
Examples of the crystalline aluminosilicate include Y-type zeolite, β zeolite, and mordenite. In particular, those obtained by modifying or stabilizing Y-type zeolite are preferred.

As a modification method of Y-type zeolite, there is a method of ion exchange with iron ions. As the physical properties of the Y-type zeolite ion-exchanged with iron ions, SiO ₂ / Al ₂ O ₃ (molar ratio) is 3.5 or more, preferably 4.6 or more. The lattice constant is preferably 24.20 to 24.40.
Moreover, as a stabilization processing method of a Y-type zeolite, the method of implementing a steaming process in water vapor | steam within the range of 540 degreeC or more and 810 degrees C or less is mentioned. Mineral acid is added to the crystalline aluminosilicate after the steaming treatment to clean the dealuminated aluminum and fallen aluminum. In the case of further modification with iron, it is preferable to add iron sulfate and mix and agitate to carry the iron supported and the dealumination and removal of the dropped aluminum.
The sixth, eighth, ninth, and tenth group metal components of the periodic table, the refractory inorganic oxide support component, and the like are the same as the catalyst used in the above-described deoxygenation treatment.
The catalyst used for the above-described deoxygenation treatment and hydrocracking treatment is preferably used after being subjected to hydrogen reduction treatment at 300 to 400 ° C. for 1 to 36 hours in a hydrogen atmosphere.

<Deoxygenation and hydrocracking treatment conditions>
In the deoxygenation treatment process and the hydrocracking treatment process, the hydrogen partial pressure is 3 MPa or more and 15 MPa or less, the liquid space velocity (LHSV) is 0.2 hr ⁻¹ or more and 3.0 hr ⁻¹ or less, and the temperature is 200 ° C. or more and 450 ° C. or less. It is preferable to implement.
The hydrogen partial pressure is preferably 3 MPa or more and 10 MPa or less, and the liquid space velocity is preferably 0.3 hr ⁻¹ or more and 2.0 hr ⁻¹ or less.
In addition, since the deoxygenation treatment step and the hydrocracking treatment step can be performed under the same conditions, both steps can be performed separately or at a time.
By this deoxygenation and hydrocracking treatment, it contains 99% by volume or more of saturated hydrocarbons based on the fuel oil base material from compounds such as anacardic acid, cardol, and cardanol contained in cashew nutshell oil, which is a raw material oil, and carbon A fuel oil base material containing at least 60% by volume of isoparaffin and naphthene of several tens to 14 based on the saturated hydrocarbon is obtained. Further, after the deoxygenation and hydrocracking treatment, further necessary fuel oil base material can be fractionated by distillation as necessary.

[Fuel oil composition]
The fuel oil composition according to the embodiment of the present invention includes the above-described fuel oil base material in an amount of 50% by volume to 100% by volume based on the fuel oil composition. The fuel oil composition according to the present embodiment is produced by adding petroleum fractions in an appropriate ratio as necessary. The fuel oil base material is contained in an amount of 1% by volume or more, preferably 50% by volume or more and 100% by volume or less, more preferably 70% by volume or more and 100% by volume or less, based on the total volume of the fuel oil composition. The remainder may contain petroleum fractions, additives applicable to the fuel oil composition, and the like.

The density at 15 ° C. of the fuel oil composition is preferably 0.75 g / cm ³ or more and 0.87 g / cm ³ or less. More preferably, 0.76 g / cm ³ or more 0.84 g / cm ³ or less, more preferably, not more than 0.765 g / cm ³ or more 0.80 g / cm ^3, most preferably 0.775 g / cm ³ or more and 0.785 g / cm ³ or less. When the density at 15 ° C. is in the above range, the calorific value required for the fuel oil composition can be increased, and the low temperature performance and combustibility can be improved. The aromatic content of the fuel oil composition is preferably 0.1% by volume or less.
The smoke point of the fuel oil composition is preferably 38 mm or more.
The deposition point of the fuel oil composition is preferably −50 ° C. or lower.
The refractive index of the fuel oil composition is preferably 1.42 or more and 1.44 or less. When the refractive index is within this range, the low temperature characteristics are excellent and a high calorific value can be obtained. From this viewpoint, the refractive index is more preferably 1.422 or more and 1.436 or less, and further preferably 1.424 or more and 1.432 or less.
The distillation properties of the fuel oil composition are such that the boiling range is 140 ° C. or higher and 300 ° C. or lower, the 10% by volume distillation temperature is 205 ° C. or lower, and the 95% distillation temperature is 268 ° C. or lower. Those having an end point of 300 ° C. or lower are preferred.

EXAMPLES Next, although an Example and a comparative example demonstrate this invention further in detail, this invention is not limited to these Examples.
[Evaluation method]
A fuel oil base was produced from the raw oil (oil extracted from cashew nut shell). Subsequently, a fuel oil composition was prepared using the produced fuel oil base material. The properties of the obtained fuel oil composition were evaluated by the following methods.
<Density at 15 ° C>
The density at 15 ° C. of the fuel oil base material and the fuel oil composition is a density measured by JIS K 2249 “Density test method and density / mass / capacity conversion table for crude oil and petroleum products”.
<Precipitation point>
Measured according to JIS K 2276 “Precipitation point test method (aviation fuel oil)”.
<Smoke point>
The measurement was performed according to JIS K 2537.
<Flash point>
(1) 1 of JIS K 2265 (tag sealed type)
(2) JIS K 2265-3 (Penschmolten sealed flash point test method)
The temperature below 60 ° C. was measured according to the test method (1), and the temperature above 60 ° C. was measured according to the test method (2).
<Distillation properties>
Distillation test: Measured according to JIS K 2254 (fuel oil distillation test method).
<Aromatic content>
Measured according to JIS K 2536 “Fuel oil hydrocarbon component test method (fluorescent indicator adsorption method)”.
<Heat generation amount>
The calorific value is a value measured or calculated according to the estimation formula (clause number 6.3e) 1) of JIS K 2279 “Crude oil and petroleum products—heating value test method and calculation estimation method”.
In addition, the calorific value of the later-described vegetable oil methyl esterified product was measured according to JIS K 2279 “Crude oil and petroleum products—a calorific value test method and a calculation estimation method”.
34.0 MJ / L or more “excellent”
Less than 34.0 MJ / L and 33.0 MJ / L or less “good”
Less than 33.0 MJ / L was set as “impossible”.
<Method for identifying C10-14 isoparaffin and naphthene>
The isoparaffin having 10 to 14 carbon atoms and the naphthene having 10 to 14 carbon atoms were identified by the following method. 7890A GC System (Agilent Technologies) was used for identification (GC-MS) and quantification (GC-FID) under the following conditions.
Column: VF-5ms (Agilent Technologies) GC-MS measurement Inlet temperature: 300 ° C
Oven temperature: 300 ° C. (heated from 40 ° C. at 6 ° C./min)
Carrier gas: He
Injection volume: 0.1 μl
<Refractive index>
The refractive index was measured according to JIS K0062.

[Manufacture of fuel oil base]
<Manufacture of catalyst>
(Manufacture of deoxygenation catalyst)
A catalyst for deoxygenation treatment was prepared with reference to JP 2010-235944 A. First, a titanium-containing aqueous solution was prepared based on International Patent Publication WO2002 / 049963. Put 12.7 g of hydrous titanium oxide powder having a titanium oxide (TiO ₂ ) ratio of 85% by mass by baking at 500 ° C. for 4 hours and 70 g of pure water in a glass beaker having an internal volume of 1 L, Stir to slurry. Next, an aqueous solution obtained by mixing 78.7 g of 35% by mass hydrogen peroxide and 26.5 g of 26% by mass ammonia water was added to the hydrous titanium oxide slurry. Then, it stirred for 3 hours, maintaining 25 degreeC, and obtained the yellow-green and transparent titanium containing aqueous solution. There, 28.4 g of citric acid monohydrate was added. Then, after hold | maintaining at the temperature of 30 degrees C or less for 6 hours, 120 g of transparent titanium containing aqueous solution by pH 6.2 was obtained by hold | maintaining at 80-95 degreeC for 12 hours. 58.5 g of the obtained titanium-containing aqueous solution was collected, diluted with pure water to 80 ml, and impregnated with 100 g of four-leaf alumina at a pore volume of 0.8 ml / g under normal pressure (pore filling method). Then, after drying for 1 hour at 70 ° C. under reduced pressure using a rotary evaporator, it was dried for 3 hours at 120 ° C. and finally calcined for 4 hours at 500 ° C. to obtain a TiO ₂ -5 mass% supported alumina carrier.
Next, 75.3 g of basic nickel carbonate (44.0 g as NiO) having a nickel oxide (NiO) ratio of 58.4% by mass obtained by firing at 500 ° C. for 4 hours, 220 g of molybdenum trioxide. Then, 250 ml of pure water was added to 34.5 g of orthophosphoric acid (29.3 g as P ₂ O ₅ ), dissolved at 80 ° C. with stirring, cooled at room temperature, and then fixed to 264 ml with pure water. A nickel-molybdenum impregnation solution was prepared. 60 milliliters of the impregnating solution was sampled, 6 g of triethylene glycol was added, diluted and constant volume with pure water to meet the water absorption of 100 g of the TiO ₂ -5 mass% supported alumina carrier, Impregnated. Subsequently, after drying under reduced pressure using a rotary evaporator at 70 ° C. for 1 hour, heat treatment was performed at 120 ° C. for 16 hours to prepare a hydrogenation catalyst 1. The composition of the hydrogenation catalyst 1, the alumina 57 wt%, TiO ₂ -3% by weight, NiO-6 mass%, MoO ₃ -30 wt%, and the P ₂ O ₅ -4 wt%.

(Manufacture of hydrocracking catalyst)
The hydrocracking catalyst was prepared with reference to JP2009-242507. First, a synthetic Na—Y zeolite (SiO ₂ / Al ₂ O ₃ molar ratio 5.0) was ammonium-exchanged to obtain NH ₄ —Y zeolite. This was steamed at 580 ° C. to obtain a steamed zeolite. After 10 kg of steaming zeolite was suspended in 115 L of pure water, the suspension was heated to 75 ° C. and stirred for 30 minutes. Next, sulfuric acid (sulfuric acid> 97% manufactured by Wako Pure Chemical Industries, Ltd.) was diluted with ion-exchanged water to this suspension, and 63.7 kg of 10% by mass sulfuric acid solution was added over 35 minutes. Further, the concentration was 0.57 mol / L. 11.5 kg of ferric sulfate solution (manufactured by Kanto Chemical Co., Ltd., 70% purity dissolved in ion-exchanged water) was added over 10 minutes. After the addition, the mixture was further stirred for 30 minutes, filtered, washed, and solids concentration 30. A 5 mass% iron-containing crystalline aluminosilicate slurry was obtained.
Next, an alumina slurry was prepared. 80 kg and 50 mass of sodium aluminate solution (a solution of Al / NaOH 0.78 manufactured by Wako Pure Chemical Industries, Ltd. dissolved in NaOH / Al ₂ O ₃ equivalent concentration 5.0 mass%) in a stainless steel container with a steam jacket with an internal volume of 200 L 240 g of a 100% gluconic acid solution (purity 50% manufactured by Kanto Chemical Co., Inc.) was added and heated to 60 ° C. Next, 88 kg of an aluminum sulfate solution (aluminum sulfate 14-18 hydrate (purity 55 wt%, manufactured by Wako Pure Chemical Industries, Ltd.) dissolved in water / Al ₂ O ₃ conversion concentration 2.5 mass%) was prepared in a separate container, 15 The diluted aluminum sulfate solution was added so that the pH became 7.2 in a minute to obtain an aluminum hydroxide slurry. The aluminum hydroxide slurry was further aged for 60 minutes while maintaining the temperature at 60 ° C. Next, the entire amount of the slurry was dehydrated with a flat plate filter and washed with 600 L of 0.3 mass% aqueous ammonia at 60 ° C. to obtain an alumina cake. A part of the alumina cake was purified water and 15% by mass of ammonia water to obtain a slurry having an alumina concentration of 12.0% by mass and a pH of 10.5. This slurry was placed in a stainless steel aging tank equipped with a refluxer and aged at 95 ° C. for 8 hours with stirring. Subsequently, pure water was added to the aging slurry, diluted to an alumina concentration of 9.0% by mass, transferred to an autoclave with a stirrer, and aged at 145 ° C. for 5 hours. Furthermore, the mixture was heated and concentrated so that the concentration in terms of Al ₂ O ₃ was 20% by mass, and deammoniated at the same time to obtain an alumina slurry. 191 g of the iron-containing crystalline aluminosilicate slurry (30.5 mass% concentration) and 2625 g of alumina slurry (20 mass% concentration) prepared in this way are added to a kneader and concentrated to a concentration that allows extrusion molding while heating and stirring. Then, it was extruded into a trilobal pellet of 1/16 inch size (about 1.6 mm). Subsequently, after drying at 110 degreeC for 16 hours, it baked at 550 degreeC for 3 hours, and obtained the support | carrier of 10/90 by iron-containing crystalline aluminosilicate / alumina (solid content conversion weight ratio).
Next, a suspension of molybdenum trioxide and nickel carbonate in pure water was heated to 90 ° C., and then malic acid was added and dissolved. The solution was charged into the above support for the whole catalyst so that it was impregnated so as to be 11% by mass as MoO _{3 and} 4% by mass as NiO, then dried and calcined at 550 ° C. for 3 hours to obtain a hydrocracking catalyst. Got.

<Manufacture of fuel oil base>
For the production of the fuel oil base material, a high-pressure fixed bed flow type bench scale reactor (total length: 500 mm) was used. The center part of the reactor was filled with 10 cc of a deoxygenated catalyst adjusted to 16 to 32 mesh, the inlet side and the outlet side were sandwiched with quartz wool, and the part other than the part filled with the catalyst was filled with ceramic balls. Before the reaction, a hydrogen reduction treatment at 360 ° C. for 24 hours was performed in a hydrogen atmosphere for catalyst activation. The deoxygenation reaction uses an oil component extracted from cashew nut shell as a raw material oil and heat-treated (cashew nut shell oil, product name “CX-1000”, manufactured by Cashew Co., Ltd., trade name “CX-1000”). LHSV = 0.5 h ⁻¹ , hydrogen / feed oil ratio = 2000 NL / L. The product is moisture and oil produced by the deoxygenation reaction. This was separated and only the oil was recovered to obtain a deoxygenated product oil.
Subsequently, the obtained deoxygenated oil was hydrocracked. The same high pressure fixed bed flow type bench scale reactor was used for hydrocracking treatment. The center part of the reactor was filled with 5 cc hydrocracking catalyst having a particle size of 16 to 32 mesh, the inlet side and the outlet side were sandwiched with quartz wool, and the part other than the part filled with the catalyst was filled with ceramic balls. Before the reaction, a hydrogen reduction treatment at 360 ° C. for 24 hours was performed in a hydrogen atmosphere for catalyst activation. The hydrocracking reaction is performed using the previously produced deoxygenated product oil as the raw material oil, under hydrogen flow, 6 MPa, reaction temperature 270 ° C., LHSV = 1.0 h ⁻¹ , hydrogen / raw material oil ratio = 1500 NL / L. It was. A fraction having a boiling point of 150 to 250 ° C. of the hydrocracked oil thus obtained was separated by distillation to obtain a fuel oil base material.

[Manufacture of fuel oil composition]
The fuel oil compositions of Examples 1, 2, and 3 were manufactured by blending petroleum-based jet fuel or petroleum-based kerosene with the fuel oil base material manufactured by the above-described method. The fuel oil composition of Example 1 is 100% by volume of the fuel oil base material produced by Production Example 1, and the fuel oil composition of Example 2 is 30% by volume of petroleum-based jet fuel, according to Production Example 1. The produced fuel oil base contains 70% by volume, and the fuel oil composition of Example 3 contains 30% by volume of petroleum-based kerosene and 70% by volume of the fuel oil base. Reference Example 1 is a general-purpose petroleum-based jet fuel, and Reference Example 2 is a general-purpose petroleum-based kerosene.

[Evaluation results]
The characteristics of the fuel oil compositions of Examples 1 to 4 and Comparative Examples 1 to 9 were evaluated by the evaluation method described above. The evaluation results are shown in Tables 1 and 2.

In Tables 1 and 2,
* 1: Petroleum-based jet fuel (ASTMD-1655 JetA-1)
* 2: Petroleum kerosene * 3: Hydrogenated biodiesel oil * 4: Fatty acid methyl ester oil * 5: Synthetic fuel

  From the results of Table 1 and Table 2, even if the fuel oil base material of the example is used as it is without mixing with other base materials, it is still a jet fuel product or a kerosene product. It turned out to be usable. It was also found that even when mixed with other base materials, it can be used as a jet fuel product or a kerosene product.

Claims (6)

Contains 99% by volume or more of saturated hydrocarbons based on fuel oil base material,
Containing isoparaffin having 10 to 14 carbon atoms and naphthene having 10 to 14 carbon atoms ,
A fuel oil base material comprising the isoparaffin having 10 to 14 carbon atoms and the naphthene having 10 to 14 carbon atoms in an amount of 60% by volume or more based on the saturated hydrocarbon. The fuel oil base material according to claim 1, comprising 90% by volume or more of the C10-14 isoparaffin and the C10-14 naphthene based on the saturated hydrocarbon.   The fuel oil base material according to claim 1 or 2, wherein the sulfur content is 1 ppm by mass or less, the aromatic content is 0.1 vol% or less, the smoke point is 38 mm or more, and the precipitation point is -50 ° C or less.   A fuel oil composition comprising the fuel oil base material according to any one of claims 1 to 3 in an amount of 50% by volume to 100% by volume based on the fuel oil composition.   The fuel oil composition according to claim 4, wherein the refractive index is 1.42 or more and 1.44 or less.   The method for producing a fuel oil base according to any one of claims 1 to 4, wherein the oil extracted from the cashew nut shell is deoxygenated and hydrocracked.