JP2017088819A - Method for producing fuel oil base - Google Patents

Abstract

PROBLEM TO BE SOLVED: To provide a method for producing a fuel oil base with high yields of jet fractions and light oil fractions.SOLUTION: In a method for producing a fuel oil base, a catalyst is obtained by reducing a catalyst precursor in which a carrier comprising titanium oxide and alumina carries at least one of the periodic table group 6 metals, and the catalyst is used for the hydrogenolysis of raw oil comprising a hydrocarbon compound derived from animals and plants.SELECTED DRAWING: None

Description

  The present invention relates to a method for producing a fuel oil base material.

  Because of problems such as global warming and fossil resource depletion, the promotion of the use of renewable energy instead of fossil fuels has been proposed. As renewable energy, in addition to the use of natural energy such as sunlight, wind power, geothermal, etc., the use of biological resources including plant resources (so-called biomass) is also being studied, and technologies for the practical application of these resources Development has been active in recent years.

  In the use of biomass, attention has been paid to the use of fats and oils produced by microalgae as fuel. When using biomass, competition with food is regarded as a problem, but if it is microalgae, it does not require farmland, so competition with food is eased, and the unit area produced by microalgae This is because the advantage is expected that the amount of perishable oil is about an order of magnitude higher than that of terrestrial plants. Thus, producing biofuel from fats and oils produced by microalgae is considered as an effective means for solving various problems.

  On the other hand, as biofuels using fats and oils, there are already methods for using fats and oils as they are (SVO; Straight Vegetable Oil), methods for bringing them closer to the properties of light oil by transesterification (FAME; Fatty Acid Methyl Ester), and the like. . However, since the fuel obtained by these methods is different from existing petroleum-based fuels, various problems have arisen in the engine, and there is a problem that it is necessary to develop a new infrastructure for dissemination. . From this point of view, the fuel produced from biomass is of the same quality as existing petroleum fuels and can be easily mixed with existing fuel (Drop-in fuel). It is hoped that there will be. In particular, for jet fuels with strict fuel quality standards that are difficult to replace with other fuels, biofuels are made from hydrodeoxygenated biomass to produce complete hydrocarbon oils (drop-in fuels of the same quality as petroleum-based fuels). The request is particularly prominent, with certification being promoted by aircraft manufacturers.

Methods for producing jet fuel and diesel oil from animal and vegetable oils and fats are already known.
For example, in Patent Documents 1 and 2, a raw material oil containing an oxygen-containing hydrocarbon compound derived from animal and plant fats and oils is hydrotreated using a first catalyst and then hydroisomerized using a second catalyst. A method of manufacturing an aviation fuel base material is disclosed.

In Non-Patent Documents 1 to 3, hydrocarbon compounds derived from animal and plant oils and fats such as squalane and botryococcene are hydrogenated using Ru / CeO ₂ catalyst, CoMo catalyst, catalyst having NiMo supported on alumina-beta zeolite, and the like. A method for producing a biofuel for degradation is disclosed.

JP 2011-52077 A JP 2011-52082 A

ChemSusChem Vol. 8 (2015), no. 15, p. 2472-2475 Biotechnology and Bioengineering Vol. 24 (1982), No. 1, p. 193-225 Proceedings of the 40th Petroleum and Petrochemical Conference, p. 192 (2010)

  However, in the method for producing an aviation fuel base material described in Patent Documents 1 and 2, by-products such as water and carbon dioxide are generated in the hydrodeoxygenation step of the first step, so chlorine dissolves in the condensed water. There is a problem of causing corrosion of the device.

On the other hand, in Non-Patent Documents 1 to 3, since a hydrocarbon compound derived from animal and plant oils and fats that do not contain oxygen atoms is used as the raw material oil, the hydrodeoxygenation step as in Patent Documents 1 and 2 is not required, By-products such as water and carbon dioxide are not generated.
However, the biofuels obtained from both have low selectivity for jet fuel and light oil, and further improvements are desired.

  This invention is made | formed in view of such a situation, and it aims at providing the manufacturing method of a fuel oil base material with the high yield of a jet fraction and a light oil fraction.

As a result of intensive studies to solve the above problems, the present inventors have found that the above problems can be solved by using a catalyst obtained by reducing a specific catalyst precursor.
The present invention has been completed based on such findings.

That is, the present invention provides the following [1] to [6].
[1] Using a catalyst obtained by reducing a catalyst precursor in which at least one of Group 6 metals of the periodic table is supported on a carrier containing titanium oxide and alumina, a hydrocarbon compound derived from animals and plants is used. A method for producing a fuel oil base material, comprising hydrocracking raw material oil.
[2] The method for producing a fuel oil base material according to [1], wherein the Group 6 metal of the periodic table is molybdenum.
[3] The method for producing a fuel oil base material according to the above [1] or [2], wherein the carrier further carries nickel or cobalt.
[4] The method for producing a fuel oil base material according to any one of [1] to [3], wherein the carrier further carries phosphorus.
[5] The animal or plant-derived hydrocarbon compound according to any one of [1] to [4], wherein the hydrocarbon compound is at least one selected from the group consisting of squalene, botryococcene, farnesene, and hydrides thereof. Manufacturing method of fuel oil base material.
[6] The method for producing a fuel oil base material according to any one of the above [1] to [5], wherein the raw material oil is hydrotreated before hydrocracking the raw material oil.

  ADVANTAGE OF THE INVENTION According to this invention, the manufacturing method of a fuel oil base material with the high yield of a jet fraction and a light oil fraction can be provided.

  The method for producing a fuel oil base material according to this embodiment includes a catalyst obtained by reducing a catalyst precursor in which at least one of the Group 6 metals of the periodic table is supported on a carrier containing titanium oxide and alumina. It is characterized by hydrocracking raw material oil containing hydrocarbon compounds derived from animals and plants.

The raw material oil used in the present embodiment includes a hydrocarbon compound derived from animals and plants. The animal and plant derived hydrocarbon compounds may be linear or branched, but those having branched chains are preferred from the viewpoint of low-temperature fluidity. Moreover, carbon number becomes like this. Preferably it is 10-35, More preferably, it is 15-35, and it is preferable that it is at least 1 sort (s) selected from the group which consists of squalene, botryococcene, farnesene, and these hydrides among them.
In addition, the said compound may be used individually by 1 type, or may be used in combination of 2 or more type.

The catalyst used in this embodiment is obtained by reducing a catalyst precursor in which at least one of Group 6 metals of the periodic table is supported on a support containing titanium oxide and alumina.
As alumina, γ-alumina is preferable. The average pores of alumina 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. When used industrially, since it is used in a large reactor, it is preferable to use a molded body so as not to cause pressure loss.

  Titanium oxide may have an anatase type structure, a rutile type structure, or an amorphous structure, but from the viewpoint of increasing the surface area, an anatase type structure or an amorphous structure is preferable.

The mass ratio of alumina and titanium oxide constituting the carrier (alumina / titanium oxide) is preferably 99/1 to 80/20, more preferably 98/2 to 85/15, and still more preferably from the viewpoint of increasing activity. 97/3 to 90/10.
The content of titanium oxide contained in the catalyst precursor is preferably 1 to 12% by mass, more preferably 1 to 9% by mass, based on the total amount of the catalyst precursor, from the viewpoint of exhibiting the effects of the present invention. More preferably, it is 2 to 6% by mass.

  Examples of the method for producing the carrier include a method of slurrying and mixing titanium oxide and alumina powder, a method of mixing respective hydroxides, and a method of impregnating alumina with an aqueous solution of titanium. Moreover, it is preferable to bake at 300-600 degreeC after the said mixing or impregnation.

As the Group 6 metal of the periodic table, molybdenum and tungsten are preferable, and molybdenum is more preferable.
The molybdenum compound supported on the carrier is preferably molybdenum trioxide, ammonium molybdate, or the like, and the tungsten compound is preferably tungsten trioxide, ammonium tungstate, or the like.
The method for supporting the compound on the carrier is not particularly limited, and an impregnation method is usually used.

The carrier preferably further supports nickel or cobalt, and nickel is particularly preferable. As a method for supporting, an impregnation method is usually used.
The nickel compound supported on the carrier is preferably nickel carbonate, basic nickel carbonate, nickel nitrate or the like, and the cobalt compound is preferably cobalt carbonate, basic cobalt carbonate or cobalt nitrate.

  The metal supported on the carrier is preferably a combination of molybdenum and nickel, or molybdenum and cobalt, and more preferably a combination of molybdenum and nickel.

The carrier preferably further supports phosphorus. As a method for supporting, an impregnation method is usually used.
As the phosphorus compound supported on the carrier, various phosphoric acids such as phosphorus pentoxide and orthophosphoric acid are preferable.

The supported amount with respect to the total amount of the catalyst precursor is, based on the oxide, at least one of molybdenum and tungsten is preferably 10 to 40% by mass, more preferably 15 to 35% by mass, and at least one of nickel and cobalt. One is preferably 1 to 10% by mass, more preferably 3 to 8% by mass, and phosphorus is preferably 1 to 10% by mass, more preferably 2 to 6% by mass.
The supported amount is determined on the assumption that all the elements constituting the catalyst precursor are oxides that are stable at room temperature and in air. For example, molybdenum (Mo) is molybdenum trioxide (MoO ₃ ), nickel (Ni) is nickel oxide (NiO), cobalt (Co) is cobaltous oxide (CoO), and phosphorus (P) is diphosphorus pentoxide (P ₂ O ₅ ), aluminum (Al) is considered aluminum oxide (Al ₂ O ₃ ), and titanium (Ti) is considered titanium oxide (IV) (TiO ₂ ). In addition, the total mass is 100 mass%, and the mass of each component is the loading amount.

The catalyst used in this embodiment can be obtained by reducing the catalyst precursor in which the compound is supported on the carrier.
The reduction treatment can be carried out in the hydrocracking reactor before the reaction. It is also possible to reduce using a reduction device and then transfer the catalyst to the hydrocracking reactor. In the latter case, move the catalyst in an atmosphere such as hydrogen or nitrogen so that it is not exposed to air, or extract and fill the reactor with the catalyst wet with an organic solvent, liquid fuel, or reaction raw material. There is a way to do it. In the case of touching the air, it is also one method to keep it as short as possible and immediately use a reaction raw material or the like in the reactor and liquid-seal it. In addition, after hydrogen reduction, a method in which the metal surface of the catalyst is passivated by gradually contacting with air and then transferred to the reactor is also possible.
The reduction treatment is preferably performed immediately before using the resulting catalyst. In the case of reduction in the reactor, usually the reduction immediately before the hydrocracking reaction is inevitably performed. However, when the catalyst is extracted and moved after the reduction by the reducing device, and the catalyst is charged into the hydrocracking reactor, it is immediately before the reaction. In some cases, it may not be possible. In this case, there is no particular problem as long as the air is not touched or the passivation is maintained.
Further, the reduction treatment is preferably performed under conditions of a temperature of 300 to 500 ° C. and a reaction time of 1 to 36 hours in a hydrogen atmosphere. There is no problem even if this hydrogen is diluted with an inert gas such as nitrogen.

A fuel oil base material containing a jet fraction and a light oil fraction with high yield can be obtained by hydrocracking the raw material oil using the catalyst.
The hydrogenolysis is preferably carried out at a hydrogen partial pressure of 3 MPa to 15 MPa, a liquid hourly space velocity (LHSV) of 0.2 hr ^{−1 to} 3.0 hr ⁻¹ , and a reaction temperature of 200 ° C. to 450 ° C.
The hydrogen partial pressure is more preferably 3 MPa to 10 MPa, the liquid space velocity is more preferably 0.3 hr ^{−1 to} 2.0 hr ⁻¹ , and the reaction temperature is 370 ° C. to 450 ° C. It is more preferable that it is below ℃.

  Prior to hydrocracking the feedstock, the feedstock can be hydrotreated. The hydrogenation treatment can be performed under the same conditions as the above-mentioned hydrocracking. However, for example, when the temperature condition is carried out at a low temperature of 50 ° C. or higher and 150 ° C. or lower, the reaction rate is reduced and the heat generation during hydrogenation is suppressed. Can be preferred.

  After the hydrocracking, the necessary fuel oil base material can be fractionally distilled by distillation as necessary.

  The fuel oil base material thus obtained preferably has a higher jet fraction yield and light oil fraction yield. Each ratio (ratio of the jet fraction and the light oil fraction) can be changed to some extent according to the demands of the manufacturer. When the reaction conditions are severe (for example, high temperature, high pressure, and low SV), the ratio of the jet fraction to the light oil fraction increases. However, in that case, the total of the jet fraction yield and the light oil fraction yield tends to decrease, so it is necessary to adopt appropriate conditions. Although it is better that the raw material conversion rate is high, in order to increase the raw material conversion rate, it is necessary to make the reaction conditions severe, so that a low-value light fraction such as naphtha is likely to be generated. In order to avoid this, it is possible to improve the total conversion rate while suppressing the generation of light fractions by recycling unreacted raw materials.

Here, the jet fraction yield, the light oil fraction yield, and the raw material conversion were defined as follows.
(1) Jet fraction yield (% by mass) = [(total mass of hydrocarbon compound having 10 to 14 carbon atoms in product) / (total mass of feedstock)] × 100
(2) Gas oil fraction yield (mass%) = [(total mass of hydrocarbon compound having 15 to 22 carbon atoms in product) / (total mass of feedstock)] × 100
(3) Raw material conversion (mass%) = [1- (unreacted raw oil mass) / (total mass of raw oil)] × 100

  The fuel oil composition obtained by the production method of the present embodiment preferably contains 5% by volume or more and 100% by volume or less, more preferably 10% by volume or more and 100% by volume or less, based on the fuel oil composition. You can get things. The fuel oil composition may contain petroleum-based fractions, additives applicable to the fuel oil composition, and the like as necessary. In addition, if regulations and standards require mixing with petroleum-based fractions and the mixing ratio is also determined, it can be handled by following them.

  As the fuel oil composition, light oil, jet fuel, gasoline and the like are preferable, and light oil and jet fuel are particularly preferable.

  Hereinafter, the present invention will be specifically described with reference to Examples and Comparative Examples. In addition, this invention is not limited to the form as described in an Example.

In the autoclave reactions of Examples and Comparative Examples, the jet fraction yield and the light oil fraction yield were calculated by the following formulas as described in paragraph [0031].
(1) Jet fraction yield (% by mass) = [(total mass of hydrocarbon compound having 10 to 14 carbon atoms in product) / (total mass of feedstock)] × 100
(2) Gas oil fraction yield (mass%) = [(total mass of hydrocarbon compound having 15 to 22 carbon atoms in product) / (total mass of feedstock)] × 100

(Production Example 1. Preparation of catalyst precursor A)
Catalyst precursor A was prepared with reference to JP 2010-235944 A. First, a titanium-containing aqueous solution was prepared based on International Patent Publication WO2002 / 049963. 12.7 g of hydrous titanium oxide powder in which the ratio of titanium oxide (IV) (TiO ₂ ) determined by baking at 500 ° C. for 4 hours is 85% by mass and 70 g of pure water are put into a glass beaker having an internal volume of 1 L. The mixture was stirred and slurried. Next, an aqueous solution obtained by mixing 78.7 g of 35% by mass hydrogen peroxide water 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 taken, diluted with pure water to 80 ml, and impregnated with 100 g of four-leaf γ-alumina with a pore volume of 0.8 ml / g under normal pressure (pore filling method) did. 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) in which the proportion of nickel oxide (NiO) determined by baking at 500 ° C. for 4 hours was 58.4% by mass, 220 g of molybdenum trioxide, 250 ml of pure water was added to 34.5 g of phosphoric acid (29.3 g as P ₂ O ₅ ), dissolved at 80 ° C. with stirring, cooled to room temperature, and then fixed to 264 ml with pure water.・ Molybdenum impregnation solution was prepared. 60 ml of the impregnating solution was sampled, 6 g of triethylene glycol was added, diluted and constant volume with pure water so as to meet the water absorption of 100 g of the TiO ₂ -5 mass% supported alumina carrier, and brought to normal pressure. Impregnated. Subsequently, after drying under reduced pressure for 1 hour at 70 degreeC using the rotary evaporator, it heat-processed for 16 hours at 120 degreeC, and the catalyst precursor A was prepared. Catalyst precursor A was 57% by mass of alumina, 3% by mass of TiO ₂ , 6% by mass of NiO, 30% by mass of MoO _{3 and} 4% by mass of P ₂ O _{5 in} terms of charge.

(Production Example 2. Preparation of catalyst precursor B)
75.3 g of basic nickel carbonate (44.0 g as NiO) having a proportion of nickel oxide (NiO) of 58.4% by mass, 220 g of molybdenum trioxide, 34.5 g of normal phosphoric acid (29. as P ₂ O ₅₎ . 3 g), 250 ml of pure water was added and dissolved at 80 ° C. with stirring. After cooling at room temperature, a nickel / molybdenum impregnating solution having a constant volume of 264 ml with pure water was prepared. 60 ml of the impregnating solution was collected, 6 g of triethylene glycol was added, and an alumina carrier (commercially pseudoboehmite alumina powder (Cataloid AP, manufactured by JGC Catalysts & Chemicals Co., Ltd.) was calcined at 500 ° C. for 5 hours. (Alumina) Diluted and constant volume with pure water so as to match the water absorption of 100 g, impregnated at normal pressure, then dried under reduced pressure using a rotary evaporator at 70 ° C. for 1 hour, then 120 ° C. For 16 hours to prepare catalyst precursor B. Catalyst precursor B is 60% by mass of alumina, 6% by mass of NiO, 30% by mass of MoO _{3 and} 4% by mass of P ₂ O _{5 in} terms of charge. Met.

(Production Example 3. Production of catalyst precursor C)
Catalyst precursor C was prepared with reference to JP2009-242507A. First, the 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 (manufactured by Wako Pure Chemical Industries, Ltd., sulfuric acid> 97%) was diluted with ion-exchanged water and 63.7 kg of a 10% by mass sulfuric acid solution was added to the suspension over 35 minutes, and the concentration was further reduced to 0.00. 11.5 kg of a 57 mol / L ferric sulfate solution (manufactured by Kanto Chemical Co., Ltd., 70% purity dissolved in ion-exchanged water) was added over 10 minutes, and after addition, stirring was continued for 30 minutes, followed by filtration. Washing was performed to obtain an iron-containing crystalline aluminosilicate slurry having a solid content concentration of 30.5% by mass.

Next, an alumina slurry was prepared. A sodium aluminate solution (Wako Pure Chemical Industries, Ltd., molar ratio (Al / NaOH) 0.78 dissolved in sodium hydroxide) in a stainless steel container with a steam jacket having an internal volume of 200 L / concentration equivalent to Al ₂ O ₃ (5.0% by mass) 80 kg and 50% by mass of a gluconic acid solution (manufactured by Kanto Chemical Co., Inc., purity 50%) 240 g were added and heated to 60 ° C. Next, 88 kg of aluminum sulfate solution (aluminum sulfate 14-18 hydrate (manufactured by Wako Pure Chemical Industries, Ltd., purity 55 wt%) dissolved in water / Al ₂ O ₃ equivalent concentration 2.5 mass%) in a separate container The diluted aluminum sulfate solution was added so that the pH became 7.2 in 15 minutes 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. Further, the mixture was heated and concentrated so as to be 20% by mass in terms of Al ₂ O _{3, and} deammonied 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 the iron containing crystalline aluminosilicate / alumina (solid content conversion mass 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-mentioned carrier with respect to 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 catalyst precursor C. Obtained. Catalyst precursor C was 76.5% by mass of alumina, 8.5% by mass of zeolite, 4% by mass of NiO, and 11% by mass of MoO _{3 in} terms of charge.

Example 1
A predetermined amount (0.25 g) of the catalyst precursor A prepared in Production Example 1 was measured, and this was subjected to a reduction treatment in a hydrogen stream in a flow system reaction apparatus to obtain Catalyst A. The hydrogen flow rate during the reduction treatment was 100 cc / min, and the hydrogen pressure was 0.2 MPa. Further, the reduction temperature of the catalyst precursor A was 400 ° C., the temperature increase rate was 7 ° C./min, and the reduction time was 2 hours.

A swing type autoclave reactor was used for the hydrocracking reaction. This batch-type reaction apparatus is an apparatus that can achieve high stirring efficiency by swinging the entire apparatus. A predetermined amount (1.35 g) of squalane (manufactured by Wako Pure Chemical Industries, Ltd.) was introduced into the glass inner tube of this apparatus, and catalyst A was liquid-sealed therein. The inner tube into which the catalyst A was introduced was introduced into the reactor and sealed. 4.5 MPa hydrogen was squeezed here and fixed to the reactor. The H ₂ / oil ratio was 1004 NL / L. The reaction apparatus was heated to the reaction temperature in a stationary state. The reaction temperature was 400 ° C., and the heating rate was 5 ° C./min. The total pressure at this reaction temperature was about 7 MPa. After confirming that the predetermined temperature was reached, the swing of the reaction apparatus was started to start the reaction. The reaction time was 1 hour, the swing was stopped when the reaction time was reached, and the reaction was stopped.
After completion of the reaction, the reaction tube was taken out from the reaction apparatus and allowed to cool, and then the glass inner tube was collected. The product was dissolved in a glass inner tube using 6 mL of carbon disulfide, and the product was recovered. The recovered product was analyzed using a GC-FID apparatus. In addition, about the produced | generated gas fraction, it collect | recovered at the time of extraction of a glass inner tube, and analyzed using the GC-TCD apparatus.
The reaction results are shown in Table 1.

(Example 2)
The reaction was performed in the same manner as in Example 1 except that the raw material squalane was changed to 1.00 g, the catalyst precursor A was changed to 0.50 g, and the H ₂ / oil ratio was changed to 1353 NL / L. The reaction results are shown in Table 1.

(Example 3)
The reaction was conducted in the same manner as in Example 1 except that the reaction temperature was changed to 360 ° C. The reaction pressure was about 6.7 MPa. The reaction results are shown in Table 2.

Example 4
The reaction was conducted in the same manner as in Example 1 except that the raw material was changed to squalene (manufactured by Wako Pure Chemical Industries, Ltd.) in Example 1 and the H ₂ / oil ratio was changed to 1067 NL / L. The reaction results are shown in Table 3.

(Comparative Example 1)
A predetermined amount (0.25 g) of the catalyst precursor B obtained in Production Example 2 was measured, and this was subjected to reduction treatment in a flow system reactor under a hydrogen stream, whereby Catalyst B was obtained. The hydrogen flow rate during the reduction treatment was 100 cc / min, and the hydrogen pressure was 0.2 MPa. Further, the reduction temperature of the catalyst precursor B was 400 ° C., the temperature increase rate was 7 ° C./min, and the reduction time was 2 hours.
Next, the reaction was performed in the same manner as in Example 1 except that the catalyst B obtained above was used as the catalyst. The reaction results are shown in Table 1.

(Comparative Example 2)
Catalyst precursor C 0.25 g, squalane (Wako Pure Chemical Industries, Ltd.) 1.35 g, and dimethyl disulfide (Wako Pure Chemical Industries, Ltd.) 47.2 μL were introduced into an autoclave glass inner tube ( Sulfurization treatment).
The inner tube was introduced into the reactor and sealed. 4.5 MPa hydrogen was squeezed here and fixed to the reactor. The H ₂ / oil ratio was 1004 NL / L. Thereafter, the temperature of the reaction apparatus was increased to 250 ° C. at a temperature increase rate of 5 ° C./min, maintained at 250 ° C. for 60 minutes, and then heated to a reaction temperature of 400 ° C. at a temperature increase rate of 5 ° C./min. Otherwise, the reaction was carried out in the same manner as in Example 1. The reaction results are shown in Table 1.

(Comparative Example 3)
Catalyst precursor A 0.25 g, squalane (Wako Pure Chemical Industries, Ltd.) 1.35 g, and dimethyl disulfide (Wako Pure Chemical Industries, Ltd.) 143.6 μL were introduced into an autoclave glass inner tube ( Sulfurization treatment).
The inner tube was introduced into the reactor and sealed. 4.5 MPa hydrogen was squeezed here and fixed to the reactor. The H ₂ / oil ratio was 1004 NL / L. Thereafter, the temperature of the reaction apparatus was raised to 250 ° C. at a temperature rising rate of 5 ° C./min, maintained at 250 ° C. for 60 minutes, and then heated to a reaction temperature of 360 ° C. at a temperature rising rate of 5 ° C./min. At this time, the reaction pressure was about 6.7 MPa. Otherwise, the reaction was carried out in the same manner as in Example 1. The reaction results are shown in Table 2.

Compared with Comparative Example 1 in which the carrier is only alumina, in Example 1 in which titanium oxide is present in the carrier, the total yield of the jet fraction and the light oil fraction is high. Further, in Example 2 in which the amount of catalyst was increased, the amount of raw material was decreased, and the ratio of hydrogen to the raw material was increased as compared with Example 1, the reaction proceeded more and the jet fraction yield and the light oil fraction yield were increased. The total yield was 61.5% by mass, which was higher than that of Example 1.
On the other hand, in Comparative Example 2 in which zeolite was present on the support and a catalyst that had been subjected to sulfurization treatment instead of reduction treatment was likely to be excessively decomposed, the total yield of jet fraction and light oil fraction yield was 5 It was very low as 0.0 mass%.
Next, see Table 2. Example 3 is also less active because the reaction temperature was 360 ° C., but in Comparative Example 3 using a catalyst that was not subjected to reduction treatment and was subjected to sulfurization treatment, the total of the jet fraction and light oil fraction yield was obtained. The yield was as low as 1.1% by mass.
Moreover, in Example 4 which used squalene as a raw material shown in Table 3, the very high jet fraction yield and the light oil fraction yield were obtained.

Claims (6)

Using a catalyst formed by reducing a catalyst precursor in which at least one of Group 6 metals of the periodic table is supported on a support containing titanium oxide and alumina,
A method for producing a fuel oil base material, comprising hydrocracking a feedstock containing a hydrocarbon compound derived from animals and plants.   The method for producing a fuel oil base material according to claim 1, wherein the Group 6 metal of the periodic table is molybdenum.   The method for producing a fuel oil base material according to claim 1 or 2, wherein the carrier further carries nickel or cobalt.   The method for producing a fuel oil base according to any one of claims 1 to 3, wherein the carrier further carries phosphorus.   The fuel oil base material according to any one of claims 1 to 4, wherein the animal and plant-derived hydrocarbon compound is at least one selected from the group consisting of squalene, botryococcene, farnesene, and hydrides thereof. Manufacturing method.   The method for producing a fuel oil base material according to any one of claims 1 to 5, wherein the raw material oil is hydrotreated before hydrocracking the raw material oil.