JP5349213B2 - Aviation fuel oil base material production method and aviation fuel oil composition - Google Patents

Abstract

<P>PROBLEM TO BE SOLVED: To provide a method for producing an aviation fuel oil base material originating from an animal and vegetable oil which has a high yield of the aviation fuel oil base material and exhibits excellent low temperature performance. <P>SOLUTION: The method for producing the aviation fuel oil base material includes: a first step of hydrogenating raw oil containing a mixture of two or more kinds of animal and vegetable oil having different fatty acid composition and a sulfur-containing hydrocarbon compound in the presence of hydrogen; and a second step of hydroisomerizing the hydrogenated oil obtained in the first step in the presence of hydrogen. In the mixture of the animal and vegetable oil, the total content of each fatty acid composition having a 9-15C fatty acid carbon chain is 50-70 mass% and the ratio of respective fatty aid compositions having a 11C, a 13C and 15C fatty acid carbon chain is 10-60 when total content of fatty acid composition having a 9-15C fatty acid carbon chain is defined as 100. <P>COPYRIGHT: (C)2011,JPO&amp;INPIT

Description

  The present invention relates to a method for producing an aviation fuel oil base and an aviation fuel oil composition.

Attention has been focused on the effective use of biomass energy as a measure to prevent global warming. Among them, biomass energy derived from plants can effectively use carbon immobilized from carbon dioxide in the atmosphere by photosynthesis during the growth process of plants, so it does not lead to an increase in carbon dioxide in the atmosphere from the viewpoint of the life cycle, so-called It has the property of being carbon neutral.
Also in the field of aviation fuel, if biomass-derived fuel oil can be used, it will play an effective role in reducing carbon dioxide emissions. As fuel oils using animal and vegetable oils, fatty acid methyl ester oils (abbreviated as “FAME” from the acronym of Fatty Acid Methyl Ester) are generally known. FAME is produced by subjecting triglyceride, which is a general structure of animal and vegetable oils, to transesterification with methanol by the action of an alkali catalyst or the like.
However, in the process for producing FAME, as described in Patent Document 1 below, it is necessary to treat glycerin produced as a by-product, and problems such as cost and energy are required for cleaning the produced oil. ing.
Also, FAME has two oxygen atoms in one molecule, so it has an extremely high oxygen content as a fuel. Even when blended with conventional diesel fuel derived from petroleum, this oxygen content is still in the engine. There is also a problem that adverse effects on materials are concerned.
Therefore, a method for producing a fuel oil composed of hydrocarbons substantially free of oxygen by hydrodeoxygenating raw material oils containing oxygenated hydrocarbon compounds derived from animals and plants in the presence of a hydrogenation catalyst is studied. (For example, see Patent Documents 1 and 2).

JP 2003-171670 A JP 2007-308563 A

However, the conventional manufacturing method has room for improvement in the following points.
That is, since the fatty acid contained in the animal and plant oil has a carbon number unique to that animal and plant, the carbon number of the fatty acid contained in the animal and plant oil used as a raw material is biased. And when the hydrogenation process is performed using animal and vegetable oils with a biased carbon number of fatty acids as a raw material oil, the resulting aviation fuel oil base material will also have a biased carbon number. Aviation fuel base materials with a biased number of carbons, whether used alone or mixed with petroleum-derived aviation fuel base materials having a continuous carbon number distribution, The deposition point is higher than that of an aviation fuel base material having a typical carbon number distribution, and there is a concern that the low temperature performance of aviation fuel oil may be deteriorated.
The present invention has been made in view of the above-described problems of the prior art, and provides a method for producing an aviation fuel oil base material derived from animal and vegetable oils that has a high aviation fuel oil base material yield and excellent low-temperature performance. With the goal.

  That is, the present invention includes a first step of hydrotreating a mixture of two or more animal and vegetable oils and fats having different fatty acid compositions and a feedstock oil containing a sulfur-containing hydrocarbon compound in the presence of hydrogen, A second step of hydroisomerizing the hydrotreated oil obtained in the step in the presence of hydrogen, and each fatty acid composition having a fatty acid carbon chain having 9 to 15 carbon atoms in the mixture of animal and vegetable oils and fats The total amount of the fatty acid is 50 to 70% by mass, and the fatty acid composition total amount having a fatty acid carbon chain having 9 to 15 carbon atoms is 11, and the fatty acid carbon chain having 13 carbon atoms and 15 carbon atoms is defined. It is related with the manufacturing method of the aviation fuel oil base material characterized by the ratio of each fatty acid composition being 10-60.

In the present invention, the first step comprises mixing a mixture of two or more animal and vegetable oils and fats having different fatty acid compositions in the presence of hydrogen, and a raw material oil containing a sulfur-containing hydrocarbon compound, with aluminum, silicon, zirconium, A porous inorganic oxide comprising two or more elements selected from boron, titanium, and magnesium, and 1 selected from elements of Groups 6A and 8 of the periodic table supported on the porous inorganic oxide Under the conditions of hydrogen pressure 2-13 MPa, liquid space velocity 0.1-3.0 h ⁻¹ , hydrogen / oil ratio 150-1500 NL / L, reaction temperature 150-480 ° C. The aviation fuel oil as described above, comprising a step of hydrotreating the raw oil and removing hydrogen, hydrogen sulfide, carbon dioxide and water from the obtained material to obtain a hydrotreated oil. A process for the production of wood.

Further, in the present invention, in the second step, the hydrotreated oil obtained in the first step is further selected from aluminum, silicon, zirconium, boron, titanium, magnesium and zeolite in the presence of hydrogen. Using a catalyst comprising a support made of a porous inorganic oxide comprising a metal selected from Group 8 elements of the periodic table, a hydrogen pressure of 2 to 10 MPa, a liquid space velocity of 0.1 to 3.0 h ^-1 , a process for hydroisomerization under the conditions of a hydrogen / oil ratio of 100-1500 NL / L and a reaction temperature of 250-330 ° C.

  Furthermore, this invention relates to the aviation fuel oil composition containing the aviation fuel base material manufactured with the said manufacturing method.

  INDUSTRIAL APPLICABILITY According to the present invention, there is provided a method for producing an aviation fuel oil base material derived from animal and vegetable oils having a high base material yield and excellent low-temperature performance, using a mixture of two or more kinds of animal and vegetable oils and fats having different fatty acid compositions as raw materials. .

Hereinafter, the present invention will be described in detail.
In the method for producing an aviation fuel base material of the present invention, a mixture of two or more kinds of animal and vegetable oils and fats having different fatty acid compositions and a sulfur-containing hydrocarbon compound are used as a raw material oil.

  Animal and vegetable oils and fats are oils and fats derived from animal oils and / or vegetable oils. Examples of animal oils include beef tallow, milk lipid (butter), pork tallow, sheep fat, whale oil, fish oil, liver oil, and the like. , Palm palm, olives, red rice, rapeseed (rapeseed), rice bran, sunflower, cottonseed, corn, soybean, jatropha, sesame, flaxseed, seeds and other parts of algae, oils produced by certain microalgae Or hydrocarbons. Specific microalgae means algae that have the property of converting a part of nutrients in the body into a hydrocarbon or oil form, such as chlorella, squid damo, spirulina, euglena, botriococcus brownie, pseudocollistis Ellipsoidia can be mentioned. Chlorella, squid damo, spirulina and euglena are known to produce oils and fats, and Botriococcus brownie and pseudocollistis ellipsoidia are known to produce hydrocarbons. In this invention, 2 or more types of mixtures chosen from these animal and vegetable fats and oils are used.

These animal and vegetable oils and fats are mainly fatty acid triglycerides, and representative examples of fatty acids constituting these fatty acid triglycerides include butyric acid (C ₃ H) which is a fatty acid having no unsaturated bond in a molecular structure called saturated fatty acid. ₇ COOH), caproic acid _{(C 5} H 11 COOH), caprylic acid _{(C 7} H 15 COOH), capric acid _{(C 9} H 19 COOH), lauric acid _{(C 11} H 23 COOH), myristic acid _{(C 13} H ₂₇ COOH), palmitic acid (C ₁₅ H ₃₁ COOH), stearic acid (C ₁₇ H ₃₅ COOH), and oleic acid (C ₁₇ H ₃₃ COOH), which is an unsaturated fatty acid having one or more unsaturated bonds, linole acid _{(C 17} H 31 COOH), linolenic acid _{(C 17} H 29 COOH), ricinoleic acid ( ₁₇ H ₃₂ (OH) COOH) and the like.

Animal and vegetable fats and oils have a fatty acid composition unique to each animal and plant. For example, palm oil is mainly composed of palmitic acid, oleic acid, and linoleic acid, and coconut oil is mainly composed of lauric acid, myristic acid, and palmitic acid.
Accordingly, hydrocarbons obtained by hydrotreating a single animal or vegetable oil or fat are not preferable because of an uneven carbon number distribution. Therefore, in the present invention, in order to reduce the bias in the carbon number distribution, two or more kinds of animal and vegetable fats and oils are mixed, and the total amount of each fatty acid composition having a fatty acid carbon chain having 9 to 15 carbon atoms relative to the total fatty acid composition in the mixture. Is 50-70 mass%, and each fatty acid having 11 carbon atoms, 13 carbon atoms, and 15 carbon atoms fatty acid carbon chain when the total amount of fatty acid composition having 9 to 15 carbon atoms is 100. It is important that the composition ratio is 10-60.
When the total amount of each fatty acid composition having a fatty acid carbon chain having 9 to 15 carbon atoms is less than 50% by mass, it is not preferable because the fraction serving as the aviation fuel oil base is reduced, and when it exceeds 70% by mass, Unevenness of the carbon number distribution of the fatty acid is not preferable.
Moreover, when the total amount of fatty acid composition having a fatty acid carbon chain having 9 to 15 carbon atoms is defined as 100, the proportion of each fatty acid composition having a fatty acid carbon chain having 11 carbon atoms, 13 carbon atoms and 15 carbon atoms is 10 to 60. If it is out of the range, the deviation of the carbon number distribution of the fatty acid in the mixture becomes large, which is not preferable.

  The fatty acid composition is methyl prepared according to the standard oil analysis method (established by the Japan Oil Chemists' Society) (1991) “2.4.20.2-91 Preparation of fatty acid methyl ester (boron trifluoride-methanol method)”. Establish the ester oil analysis test method (established by the Japan Oil Chemists' Society) (1993) “2.4.21.3-77 fatty acid composition (FID temperature rising gas romatograph) using a temperature rising gas chromatograph equipped with a flame ionization detector (FID). It is a value obtained according to “method)” and indicates the constituent ratio (% by mass) of each fatty acid group constituting the oil or fat.

  The sulfur-containing hydrocarbon compound in the raw material oil plays a role of improving the deoxygenation activity in the hydrotreatment. Although it does not restrict | limit especially as a sulfur-containing hydrocarbon compound, Specifically, sulfide, disulfide, polysulfide, thiol, thiophene, benzothiophene, dibenzothiophene, these derivatives, etc. are mentioned. The sulfur-containing hydrocarbon compound contained in the feedstock oil may be a single compound or a mixture of two or more. Furthermore, a petroleum hydrocarbon fraction containing a sulfur content can also be used as the sulfur-containing hydrocarbon compound.

  As the petroleum hydrocarbon fraction containing sulfur, a fraction obtained in a general petroleum refining process can be used. For example, kerosene fraction obtained from atmospheric distillation equipment or vacuum distillation equipment, or kerosene fraction obtained from hydrodesulfurization equipment, hydrocracking equipment, residual oil direct desulfurization equipment, fluid catalytic cracking equipment, etc. May be. In addition, you may use the fraction obtained from each said apparatus individually by 1 type or in mixture of 2 or more types.

  Content of a sulfur-containing hydrocarbon compound is 1-50 mass ppm in conversion of a sulfur atom with respect to the oxygen-containing hydrocarbon compound derived from animal and vegetable oil, Preferably it is 5-30 mass ppm, More preferably, it is 10-20 mass. ppm. When the content is less than 1 ppm by mass in terms of sulfur atom, it tends to be difficult to stably maintain the deoxygenation activity. On the other hand, when it exceeds 50 mass ppm, in addition to the sulfur concentration in the light gas discharged in the hydrotreating step, the sulfur content contained in the oil to be treated or the hydrocarbon oil tends to increase. . In addition, the sulfur content in this invention means the mass content of the sulfur content measured based on the method of JISK2541 "Sulfur content test method" or ASTM-5453.

In the hydrotreatment of the first step according to the present invention, a porous inorganic oxide comprising two or more elements selected from aluminum, silicon, zirconium, boron, titanium and magnesium, and the porous inorganic A catalyst containing one or more metals selected from Group 6A and Group 8 elements of the periodic table supported on an oxide is used.
As the catalyst carrier used in the present invention, a porous inorganic oxide comprising two or more selected from aluminum, silicon, zirconium, boron, titanium and magnesium as described above is used. The porous inorganic oxide needs to be at least two selected from aluminum, silicon, zirconium, boron, titanium and magnesium from the viewpoint that the deoxygenation activity and desulfurization activity can be further improved, preferably aluminum. And an inorganic oxide (a composite oxide of aluminum oxide and another oxide).

  When the porous inorganic oxide contains aluminum as a constituent element, the aluminum content is preferably 1 to 97% by mass, more preferably 10 to 97% by mass in terms of alumina, based on the total amount of the porous inorganic oxide. %, More preferably 20 to 95% by mass. When the aluminum content is less than 1% by mass in terms of alumina, physical properties such as carrier acid properties are not suitable, and sufficient deoxidation activity and desulfurization activity tend not to be exhibited. On the other hand, when the aluminum content exceeds 97% by mass in terms of alumina, the catalyst surface area becomes insufficient and the activity tends to decrease.

The method for introducing silicon, zirconium, boron, titanium and magnesium, which are carrier constituent elements other than aluminum, is not particularly limited, and a solution containing these elements may be used as a raw material. For example, for silicon, silicon, water glass, silica sol, etc., for boron, boric acid, etc., for phosphorus, phosphoric acid and alkali metal salts of phosphoric acid, etc., for titanium, titanium sulfide, titanium tetrachloride and various alkoxide salts, etc. As for zirconium, zirconium sulfate and various alkoxide salts can be used.
Furthermore, the porous inorganic oxide preferably contains phosphorus as a constituent element. The phosphorus content is preferably 0.1 to 10% by mass, more preferably 0.5 to 7% by mass, and still more preferably 2 to 6% by mass, based on the total amount of the porous inorganic oxide. When the phosphorus content is less than 0.1% by mass, sufficient deoxygenation activity and desulfurization activity tend not to be exhibited, and when it exceeds 10% by mass, excessive decomposition proceeds and the target hydrocarbon Oil yield may be reduced.

  It is preferable to add the raw materials for the carrier constituents other than the above-described aluminum oxide in the step prior to the firing of the carrier. For example, after adding the said raw material previously to aluminum aqueous solution, the aluminum hydroxide gel containing these structural components may be prepared, and the said raw material may be added with respect to the prepared aluminum hydroxide gel. Alternatively, the above raw materials may be added in a step of adding water or an acidic aqueous solution to a commercially available aluminum oxide intermediate or boehmite powder and kneading them, but it is more preferable to coexist at the stage of preparing aluminum hydroxide gel. Although the mechanism of the effect of the carrier constituents other than aluminum oxide has not necessarily been elucidated, it is presumed that it forms a complex oxide state with aluminum, which increases the surface area of the carrier and the interaction with the active metal. It is considered that the activity is affected by producing the action.

  The porous inorganic oxide as a carrier supports one or more metals selected from Group 6A and Group 8 elements of the periodic table. Among these metals, it is preferable to use a combination of two or more metals selected from cobalt, molybdenum, nickel and tungsten. Examples of suitable combinations include cobalt-molybdenum, nickel-molybdenum, nickel-cobalt-molybdenum, and nickel-tungsten. Of these, combinations of nickel-molybdenum, nickel-cobalt-molybdenum, and nickel-tungsten are more preferred. In the hydrotreatment, these metals are used after being converted to a sulfide state.

  As the content of the active metal based on the catalyst mass, the range of the total supported amount of tungsten and molybdenum is preferably 12 to 35% by mass in terms of oxide, and more preferably 15 to 30% by mass. If the total supported amount of tungsten and molybdenum is less than 12% by mass, the active sites tend to decrease and sufficient activity cannot be obtained. On the other hand, when it exceeds 35% by mass, the metal is not effectively dispersed and sufficient activity tends to be not obtained. The range of the total supported amount of cobalt and nickel is preferably 1.0 to 15% by mass and more preferably 1.5 to 12% by mass in terms of oxide. When the total supported amount of cobalt and nickel is less than 1.0% by mass, a sufficient promoter effect cannot be obtained and the activity tends to decrease. On the other hand, if it exceeds 15% by mass, the metal is not effectively dispersed and sufficient activity tends not to be obtained.

  The method for incorporating these active metals into the catalyst is not particularly limited, and a known method applied when producing an ordinary desulfurization catalyst can be used. Usually, a method of impregnating a catalyst carrier with a solution containing a salt of an active metal is preferably employed. In addition, an equilibrium adsorption method, a pore-filling method, an incident-wetness method, and the like are also preferably employed. For example, the pore-filling method is a method in which the pore volume of the carrier is measured in advance and impregnated with a metal salt solution having the same volume. The impregnation method is not particularly limited, and it can be impregnated by an appropriate method according to the amount of metal supported and the physical properties of the catalyst carrier.

  In the present invention, the number of types of hydrotreating catalyst used is not particularly limited. For example, one type of catalyst may be used alone, or a plurality of catalysts having different active metal species and carrier components may be used. As a suitable combination in the case where a plurality of different catalysts are used, for example, a catalyst containing cobalt-molybdenum after a catalyst containing nickel-molybdenum, and nickel-cobalt-molybdenum after a catalyst containing nickel-molybdenum are used. Examples thereof include a catalyst containing nickel, a catalyst containing nickel-cobalt-molybdenum after the catalyst containing nickel-tungsten, and a catalyst containing cobalt-molybdenum after the catalyst containing nickel-cobalt-molybdenum. A nickel-molybdenum catalyst may be further combined before and / or after these combinations.

In the case of combining a plurality of catalysts having different support components, for example, the content of aluminum oxide is included in the subsequent stage of the catalyst having an aluminum oxide content of 30% by mass or more and less than 80% by mass based on the total mass of the support. A catalyst having an amount in the range of 80 to 99% by mass may be used.
Each catalyst used in the present invention can be used after preliminary sulfidation in the same manner as a general hydrodesulfurization catalyst. For example, using a hydrotreated oil or hydroisomerized oil obtained in the process of the present invention to which a sulfur-containing hydrocarbon compound is added, heat at 200 ° C. or higher is applied in a predetermined procedure under hydrogen pressure conditions. Give according to. As a result, the active metal on the catalyst becomes sulfided and exhibits activity. Although it does not restrict | limit especially as a sulfur-containing hydrocarbon compound, Specifically, sulfide, disulfide, polysulfide, thiol, thiophene, benzothiophene, dibenzothiophene, these derivatives, etc. are mentioned. These sulfur-containing hydrocarbon compounds may be a single compound or a mixture of two or more. Further, a petroleum hydrocarbon fraction containing a sulfur content may be used directly.
The preliminary sulfidation may be performed in the same reactor as the hydrotreating, or a catalyst that has been pretreated with sulfidation or that has been activated with a sulfur-containing, oxygen-containing, or nitrogen-containing organic solvent is used. You can also

  In addition to the hydrotreating catalyst, a guard catalyst and a demetallizing catalyst are provided for the purpose of trapping the scale that flows along with the feedstock as needed and supporting the hydrotreating catalyst at the separation part of the catalyst bed. Inert packing may be used. In addition, these can be used individually or in combination.

The pore volume by the nitrogen adsorption BET method of the catalyst used in the present invention is preferably 0.30 to 0.85 ml / g, and more preferably 0.45 to 0.80 ml / g. When the pore volume is less than 0.30 ml / g, the dispersibility of the supported metal becomes insufficient, and there is a concern that the active sites may decrease. Moreover, when the pore volume exceeds 0.85 ml / g, the catalyst strength becomes insufficient, and the catalyst may be pulverized or crushed during use.
Moreover, it is preferable that the average pore diameter of a catalyst is 5-11 nm, and it is more preferable that it is 6-9 nm. If the average pore diameter is less than 5 nm, the reaction substrate may not sufficiently diffuse into the pores, and the reactivity may be reduced. On the other hand, if the average pore diameter exceeds 11 nm, the pore surface area decreases, and the activity may be insufficient.
Furthermore, in the above catalyst, the ratio of the pore volume derived from pores having a pore diameter of 3 nm or less to the total pore volume is 35 volumes in order to maintain effective catalyst pores and exhibit sufficient activity. % Or less is preferable.

  Moreover, the hydrogen pressure at the time of making said raw material oil and a catalyst contact in presence of hydrogen needs to be 2 Mpa or more and 13 Mpa or less, Preferably it is 3-10 Mpa. If the hydrogen pressure exceeds 13 MPa, an excessive investment in equipment such as a compressor may be required, which is not preferable. On the other hand, when the hydrogen pressure is less than 2 MPa, the reactivity tends to decrease or the activity tends to decrease rapidly.

In the hydrogenation process, the liquid hourly space velocity (LHSV) is preferably from 0.1～3.0H ^-1, more preferably 0.7~2.5h ^-1. As the liquid space velocity is higher, the selectivity of the decarboxylation reaction is improved, but the reactivity tends to decrease, so it is not appropriate to exceed 3.0 h ⁻¹ . On the other hand, lowering the liquid space velocity causes an increase in the amount of catalyst, that is, an increase in the size of the reactor. Therefore, it is realistic to set it to 0.1 h ⁻¹ or more.

The hydrogen oil ratio (hydrogen / oil ratio) in the hydrotreatment is preferably in the range of 150 to 1500 NL / L, more preferably in the range of 200 to 1200 NL / L, and in the range of 250 to 1000 NL / L. Is particularly preferred. When the hydrogen oil ratio exceeds the above upper limit, the effect of increasing the ratio of decarboxylation reaction at the hydrogen pressure is inhibited. When the hydrogen oil ratio is below the lower limit, there is a possibility that sufficient hydrogenation reaction does not proceed.
The reaction temperature in the hydrotreatment is preferably in the range of 150 to 480 ° C, more preferably in the range of 200 to 380 ° C, and particularly preferably in the range of 250 to 365 ° C. When the reaction temperature is lower than 150 ° C., sufficient hydrogenation reaction does not proceed, and when it is higher than 480 ° C., excessive decomposition, polymerization of raw material oil, and other side reactions may proceed.

As the type of the reactor, a fixed bed system can be adopted. That is, hydrogen can adopt either a countercurrent or a cocurrent flow with respect to the feedstock. Moreover, it is good also as a form which combined the countercurrent and the parallel flow using several reactors. As a general format, it is a down flow, and a gas-liquid twin parallel flow format can be adopted. Moreover, the reactor may be used alone or in combination, and a structure in which one reactor is divided into a plurality of catalyst beds may be adopted.
The treated oil hydrotreated in the reactor is fractionated into hydrotreated oil containing a predetermined fraction through a gas-liquid separation process, a rectification process, and the like.

  By-products such as water, carbon monoxide, carbon dioxide, and hydrogen sulfide may be generated with the reaction of oxygen and sulfur contained in the feedstock oil. It is necessary to install gas-liquid separation equipment and other by-product gas removal devices in the recovery process to remove these by-products. As a device for removing by-products, a high-pressure separator or the like can be preferably exemplified.

  The spilled oil after removing the by-products may be fractionated into a plurality of fractions in a rectifying tower as necessary. For example, it may be fractionated into light fractions such as gas and naphtha fractions, middle fractions such as kerosene, jet and diesel oil fractions, and heavy fractions such as residue fractions. In this case, the cut temperature of the light fraction and the middle fraction is preferably 100 to 200 ° C, more preferably 120 to 180 ° C, and further preferably 140 to 160 ° C. Moreover, 300-400 degreeC is preferable, as for the cut temperature of a middle fraction and a heavy fraction, 300-380 degreeC is more preferable, and 300-360 degreeC is further more preferable. Moreover, hydrogen can be manufactured by reforming a part of such a light hydrocarbon fraction to be produced in a steam reformer. The hydrogen produced in this way has a characteristic of carbon neutral because the raw material used for steam reforming is a biomass-derived hydrocarbon, and can reduce the burden on the environment.

  In general, hydrogen gas is introduced from the inlet of the first reactor in association with the feed oil before or after passing through the heating furnace, but separately from this, the temperature in the reactor is controlled, Hydrogen gas may be introduced from between the catalyst beds or between a plurality of reactors for the purpose of maintaining the hydrogen pressure throughout the reactor. The hydrogen thus introduced is generally called quench hydrogen. The ratio of quench hydrogen to hydrogen gas introduced along with the feedstock oil is preferably 10 to 60% by volume, and more preferably 15 to 50% by volume. If the rate of quench hydrogen is less than 10 volumes, the reaction at the subsequent reaction site tends not to proceed sufficiently. If the rate of quench hydrogen exceeds 60% by volume, the reaction near the reactor inlet does not proceed sufficiently. Tend.

In the hydroisomerization treatment step of the second step according to the present invention, the hydrotreated oil obtained by separating the hydrogen, hydrogen sulfide, carbon dioxide and water obtained in the first step is added in the presence of hydrogen. A catalyst comprising a support made of a porous inorganic oxide composed of a substance selected from aluminum, silicon, zirconium, boron, titanium, magnesium and zeolite, and a metal selected from Group 8 elements of the periodic table is used. Then, hydroisomerization is performed under the conditions of a hydrogen pressure of 3 to 10 MPa, a liquid space velocity of 0.1 to 3.0 h ⁻¹ , a hydrogen / oil ratio of 100 to 1500 NL / L, and a reaction temperature of 250 to 330 ° C.

  The hydroisomerization catalyst is not particularly limited as long as it has hydroisomerization activity, but is a porous inorganic oxide composed of a material selected from aluminum, silicon, zirconium, boron, titanium, magnesium and zeolite, In addition, a catalyst containing one or more metal elements selected from Group 8 elements of the periodic table supported on the porous inorganic oxide is preferably used.

As the carrier of the hydroisomerization catalyst, an inorganic oxide (a composite oxide of aluminum oxide and another oxide) containing aluminum and another element is preferable from the viewpoint that the hydroisomerization activity can be further improved.
The porous inorganic oxide is more preferably configured to include at least two elements of aluminum, silicon, zirconium, and titanium. The porous inorganic oxide may be either amorphous or crystalline, and zeolite can also be used. In the case of using zeolite, it is preferable to use zeolite having a crystal structure such as FAU, BEA, MOR, MFI, MEL, MWW, TON, AEL, MTT among the structure codes defined by the International Zeolite Society.

  The metal supported on the hydroisomerization catalyst is preferably one or more metals selected from Group 8 elements of the periodic table, and among these, Pt, Pd, Ru, Rh, Au, Ir, Ni, One or more metals selected from Co are more preferable, and Pt, Rd, Ru, and Ni are particularly preferable. In addition, these active metals may combine 2 or more types of metals, for example, combinations, such as Pt-Pd, Pt-Ru, Pt-Rh, Pt-Au, Pt-Ir, are mentioned.

  The method for incorporating these active metals into the catalyst is not particularly limited, and a known method applied when producing an ordinary hydrogenation catalyst can be used. Usually, a method of impregnating a catalyst carrier with a solution containing a salt of an active metal is preferably employed. In addition, an equilibrium adsorption method, a pore-filling method, an incident-wetness method, and the like are also preferably employed. For example, the pore-filling method is a method in which the pore volume of the carrier is measured in advance and impregnated with a metal salt solution having the same volume. The impregnation method is not particularly limited, and it can be impregnated by an appropriate method according to the amount of metal supported and the physical properties of the catalyst carrier. These metals can be used as an impregnation solution by dissolving a metal source in the form of nitrate, sulfate or complex in an aqueous solution or an appropriate organic solvent.

  Further, at the hydroisomerization reaction zone inlet, the sulfur content contained in the hydroisomerization feed oil is preferably 1 mass ppm or less, more preferably 0.5 mass ppm or less. . If the sulfur content exceeds 1 mass ppm, the progress of hydroisomerization in the first step may be hindered. In addition, for the same reason, it is necessary that the reaction gas containing hydrogen introduced together with the feedstock for hydroisomerization must have a sufficiently low sulfur concentration, and is preferably 1 ppm by volume or less. More preferably, it is 5 ppm by volume or less.

The reaction conditions in the hydroisomerization step are preferably a hydrogen pressure of 2 to 10 MPa, a liquid space velocity (LHSV) of 0.1 to 3.0 h ⁻¹ , a hydrogen oil ratio (hydrogen / oil ratio) of 100 to 1500 NL / L. The reaction temperature is 250 to 330 ° C., more preferably, the hydrogen pressure is 2.5 to 8 MPa, the liquid space velocity is 0.2 to 2.5 h ⁻¹ , the hydrogen oil ratio is 200 to 1200 NL / L, and the reaction temperature is 260 to 260 ° C. More preferably, the hydrogen pressure is 3 to 7 MPa, the space velocity is 0.2 to 2.0 h ⁻¹ , the hydrogen oil ratio is 250 to 1000 NL / L, and the reaction temperature is 270 to 310 ° C. These conditions are factors that influence the reaction activity of the catalyst. For example, when the hydrogen pressure and the hydrogen oil ratio do not satisfy the above lower limit values, the reactivity decreases or the catalyst activity decreases rapidly. Tend to. On the other hand, when the hydrogen pressure and the hydrogen oil ratio exceed the above upper limit values, there is a tendency that excessive equipment investment such as a compressor is required. Further, the lower the liquid space velocity tends to be advantageous for the reaction, but if the liquid space velocity is less than the above lower limit value, there is a tendency that an extremely large internal volume reactor is required and excessive equipment investment is required, When the liquid space velocity exceeds the above upper limit, the reaction tends not to proceed sufficiently. When the reaction temperature is lower than the lower limit, sufficient hydroisomerization reaction does not proceed. When the reaction temperature is higher than the upper limit, excessive decomposition or other side reactions may proceed.

  In the hydroisomerization step, the hydrogen gas introduced into the reaction zone together with the hydroisomerization raw oil (hydrotreated oil obtained in the first step) is heated to raise the temperature to a predetermined reaction temperature. In general, it is introduced from the reaction zone inlet in the upstream or downstream of the furnace with the feedstock, but separately from this, the temperature in the reaction zone is controlled and the hydrogen pressure is maintained throughout the reaction zone. For the purpose, hydrogen gas may be introduced between the catalyst beds or between a plurality of reactors (quenched hydrogen). Alternatively, any or a combination of product oil, unreacted oil, intermediate reaction oil and the like may be combined and introduced partially from the reaction zone inlet, the catalyst bed, between the plurality of reactors, or the like. Thereby, the reaction temperature can be controlled, and an excessive decomposition reaction or reaction runaway due to an increase in the reaction temperature can be avoided.

  The aviation fuel oil base of the present invention is obtained by fractionating a fraction having a boiling point range of 140 to 300 ° C. from the hydrolyzed product oil (hydroisomerized oil) obtained through the second step. A material can be obtained.

  In order to obtain the aviation fuel base material of the present invention, the product oil after the hydroisomerization treatment is fractionated into a plurality of fractions in a rectifying column as necessary. For example, it may be fractionated into light fractions such as gas and naphtha fractions, middle fractions such as kerosene, jet and diesel oil fractions, and heavy fractions such as residue fractions. In this case, the cut temperature of the light fraction and the middle fraction is preferably 100 to 200 ° C, more preferably 120 to 180 ° C, and further preferably 140 to 160 ° C. Moreover, 300-400 degreeC is preferable, as for the cut temperature of a middle fraction and a heavy fraction, 300-380 degreeC is more preferable, and 300-360 degreeC is further more preferable. Among these, it is preferable that the aviation fuel oil base material of this invention is a fraction whose boiling point range is 140-300 degreeC. Moreover, hydrogen can be manufactured by reforming a part of such a light hydrocarbon fraction to be produced in a steam reformer. The hydrogen produced in this way has a characteristic of carbon neutral because the raw material used for steam reforming is a biomass-derived hydrocarbon, and can reduce the burden on the environment.

  In the method of the present invention, an aviation fuel oil base produced using a mixture of animal and vegetable fats and oils having different fatty acid compositions as raw materials is excellent in base yield and low temperature performance.

The aviation fuel oil composition of the present invention comprises the aviation fuel oil base material produced by the above production method.
The aviation fuel oil composition of the present invention may be composed of the aviation fuel base material obtained by the production method of the present invention alone, or may be obtained by refining other aviation fuel oil base materials such as crude oil. The aviation fuel oil composition may be mixed with the aviation fuel oil base.
The aviation fuel oil base material obtained by refining crude oil, etc. includes the aviation fuel oil fraction obtained in the general oil refining process, the synthesis gas composed of hydrogen and carbon monoxide, and the Fischer-Tropsch reaction. Synthetic fuel oil base materials obtained via the like. This synthetic fuel oil base material contains little aromatics, is characterized by saturated hydrocarbons as the main component and a high smoke point. In addition, a well-known method can be used as a manufacturing method of synthesis gas, and it is not specifically limited.

  The aviation fuel oil composition of the present invention can further contain one or more of various additives conventionally added to aviation fuel oils. Such additives include antioxidants, antistatic agents, metal deactivators, antifreezing agents and the like.

  As an antioxidant, N, N-diisopropylparaphenylenediamine, 2,6-ditertiary butylphenol is 75% or more in a range not exceeding 24.0 mg / l in order to suppress the generation of gum in aviation fuel oil. And a mixture of 25% or less of tertiary and tritertiary butylphenol, a mixture of 72% or more of 2,4-dimethyl-6-tert-butylphenol and 28% or less of monomethyl and dimethyl tertiary butylphenol, 2,4-dimethyl-6-tersia Mixtures of 55% or more of butylphenol and 45% or less of tertiary and ditertiary butylphenol, 2,6-ditertiary butyl-4-methylphenol, and the like can be added.

  As an antistatic agent, in order to prevent the accumulation of static electricity caused by friction with the inner wall of the pipe when aviation fuel oil flows inside the fuel pipe system at high speed, the range does not exceed 3.0 mg / l in order to increase the electrical conductivity. Then, STADIS 450 manufactured by Octel Co., Ltd. can be added.

  As the metal deactivator, N, N-disalicylidene is used in a range not exceeding 5.7 mg / l so that the free metal component contained in the aviation fuel oil does not react and the fuel becomes unstable. 1,2-propanediamine and the like can be added.

  As an anti-icing agent, ethylene glycol monomethyl ether or the like is added in the range of 0.1 to 0.15% by volume in order to prevent a trace amount of water contained in aviation fuel oil from freezing and blocking the pipe. be able to.

  The aviation fuel oil composition of the present invention can be appropriately blended with optional additives such as an antistatic agent, a corrosion inhibitor, and a bactericidal agent without departing from the present invention.

  The aviation fuel oil composition of the present invention preferably satisfies the standard value of JIS K2209 “aviation turbine fuel oil”.

Density at 15 ℃ aviation fuel oil composition of the present invention, from the viewpoint of fuel consumption rate, is preferably 775 kg / ^{m 3} or more, more preferably 780 kg / ^{m 3} or more. On the other hand, from the viewpoint of flammability, it is preferably 839kg / ^{m 3} or less, more preferably 830 kg / ^{m 3} or less, and more preferably 820 kg / ^{m 3} or less. Here, the density at 15 ° C. means a value measured according to JIS K2249 “Crude oil and petroleum products—density test method and density / mass / capacity conversion table”.

  The distillation property of the aviation fuel oil composition of the present invention is such that the 10% by volume distillation temperature is preferably 204 ° C. or lower, more preferably 200 ° C. or lower, from the viewpoint of evaporation characteristics. The end point is preferably 300 ° C. or less, more preferably 290 ° C. or less, and still more preferably 280 ° C. or less from the viewpoint of combustion characteristics (burn-out property). The distillation property as used herein means a value measured by JIS K2254 “Petroleum products—Distillation test method”.

  The actual gum content of the aviation fuel oil composition of the present invention is preferably 7 mg / 100 ml or less, more preferably 5 mg / 100 ml or less, from the viewpoint of preventing problems due to precipitate formation in the fuel introduction system and the like. More preferably, it is 3 mg / 100 ml or less. In addition, the real gum part here means the value measured by JIS K2261 "Gasoline and aviation fuel oil real gum test method".

  The true calorific value of the aviation fuel oil composition of the present invention is preferably 42.8 MJ / kg or more, and more preferably 45 MJ / kg or more, from the viewpoint of fuel consumption rate. In addition, the true calorific value here means a value measured according to JIS K2279 “Crude oil and fuel oil calorific value test method”.

The kinetic viscosity of the aviation fuel oil composition of the present invention is preferably such that the kinematic viscosity at −20 ° C. is 8 mm ² / s or less, and 7 mm ² / s or less from the viewpoint of fluidity of fuel piping and uniform fuel injection. More preferably, it is 5 mm < ² > / s or less. In addition, kinematic viscosity here means the value measured by JIS K2283 "Kinematic viscosity test method of crude oil and petroleum products".

  The copper plate corrosion of the aviation fuel oil composition of the present invention is preferably 1 or less from the viewpoint of the corrosiveness of the fuel tank and piping. The copper plate corrosion here means a value measured by JIS K2513 “Petroleum products—Copper plate corrosion test method”.

  The aromatic content of the aviation fuel oil composition of the present invention is preferably 25% by volume or less, and more preferably 20% by volume from the viewpoint of flammability (preventing soot generation). The aromatic content here means a value measured by JIS K2536 “Test method for fuel oil hydrocarbon components (fluorescence indicator adsorption method)”.

  The smoke point of the aviation fuel oil composition of the present invention is preferably 25 mm or more, more preferably 27 mm or more, and further preferably 30 mm or more from the viewpoint of combustibility (preventing soot generation). The smoke point here means a value measured by JIS K2537 “Fuel oil smoke point test method”.

  The sulfur content of the aviation fuel oil composition of the present invention is preferably 0.3% by mass or less, more preferably 0.2% by mass or less, and 0.1% by mass or less from the viewpoint of corrosiveness. More preferably. From the same corrosive viewpoint, the mercaptan sulfur content is preferably 0.003% by mass or less, more preferably 0.002% by mass or less, and 0.001% by mass or less. Further preferred. The sulfur content here is the value measured by JIS K2541 “Crude oil and petroleum product sulfur test method”, and the mercaptan sulfur content is measured by JIS K2276 “Mercaptan sulfur content test method (potentiometric titration method)”. Value.

  The flash point of the aviation fuel oil composition of the present invention is preferably 38 ° C. or higher, more preferably 40 ° C. or higher, and further preferably 45 ° C. or higher from the viewpoint of safety. The flash point here means a value determined by JIS K2265 “Crude oil and petroleum products—flash point test method—tag sealed flash point test method”.

  The total acid value of the aviation fuel oil composition of the present invention is preferably 0.1 mgKOH / g or less, more preferably 0.08 mgKOH / g or less, and 0.05 mgKOH / g or less from the viewpoint of corrosivity. More preferably. The total acid value here means a value measured by JIS K2276 “Total Acid Value Test Method”.

  The precipitation point of the aviation fuel oil composition of the present invention is preferably −47 ° C. or less, and preferably −48 ° C. or less, from the viewpoint of preventing a decrease in fuel supply due to fuel freezing under low temperature exposure during flight. More preferably, it is -50 degrees C or less. Here, the precipitation point means a value measured by JIS K2276 “Precipitation point test method”.

  The thermal stability of the aviation fuel oil composition of the present invention is such that the pressure difference in method A is 10.1 kPa or less, the preheating tube deposit evaluation value is less than 3, from the viewpoint of preventing fuel filter blockage due to the formation of precipitates at high temperature exposure, It is preferable that the pressure difference in the method B is 3.3 kPa or less and the preheating tube deposit evaluation value is less than 3. Here, the thermal stability means a value measured by JIS K2276 “Thermal Stability Test Method A, Method B”.

  The water solubility of the aviation fuel oil composition of the present invention is preferably 2 or less in the separated state and 1b or less in the interface state in order to prevent troubles due to precipitation of dissolved water during exposure to low temperatures. In addition, water solubility here means the value measured by JIS K2276 “water solubility test method”.

  EXAMPLES Hereinafter, although this invention is demonstrated more concretely based on an Example and a comparative example, this invention is not limited to a following example at all.

(Preparation of catalyst)
<Catalyst A>
18.0 g of water glass No. 3 was added to 3000 g of an aqueous sodium aluminate solution having a concentration of 5% by mass, and the mixture was placed in a container kept at 65 ° C. On the other hand, in another container kept at 65 ° C., a solution in which 6.0 g of phosphoric acid (concentration 85%) is added to 3000 g of an aluminum sulfate aqueous solution having a concentration of 2.5% by mass is prepared, and this contains sodium aluminate as described above. An aqueous solution was added dropwise. The time when the pH of the mixed solution reached 7.0 was set as the end point, and the resulting slurry product was filtered through a filter to obtain a cake slurry.
The cake-like slurry was transferred to a container equipped with a reflux condenser, 150 ml of distilled water and 10 g of 27% aqueous ammonia solution were added, and the mixture was heated and stirred at 75 ° C. for 20 hours. The slurry was put in a kneading apparatus and heated to 80 ° C. or higher and kneaded while removing moisture to obtain a clay-like kneaded product. The obtained kneaded material was extruded into a shape of a cylinder having a diameter of 1.5 mm by an extrusion molding machine, dried at 110 ° C. for 1 hour, and then fired at 550 ° C. to obtain a molded carrier.
50 g of the obtained shaped carrier was put into an eggplant-shaped flask, and while degassing with a rotary evaporator, 17.3 g of molybdenum trioxide, 13.2 g of nickel nitrate (II) hexahydrate, phosphoric acid (concentration 85%) An impregnation solution containing 9 g and 4.0 g malic acid was poured into the flask. The impregnated sample was dried at 120 ° C. for 1 hour and then calcined at 550 ° C. to obtain Catalyst A. Table 1 shows the physical properties of the prepared catalyst A.

<Catalyst B>
50 g of a silica-alumina carrier having a silica-alumina ratio (mass ratio) of 70:30 was placed in an eggplant-shaped flask, and a tetraammineplatinum (II) chloride aqueous solution was poured into the flask while degassing with a rotary evaporator. The impregnated sample was dried at 110 ° C. and then calcined at 350 ° C. to obtain Catalyst B. The amount of platinum supported on catalyst B was 0.5% by mass based on the total amount of catalyst.

Example 1
A first reaction tube (inner diameter 20 mm) filled with catalyst A (100 ml) was attached to a fixed bed flow reactor. A high-pressure separator was connected to the subsequent stage of the first reaction tube, and a second reaction tube (inner diameter 20 mm) filled with catalyst B (50 mL) was connected to the destination of the spilled oil from the high-pressure separator. Thereafter, for catalyst A, a straight-run gas oil to which dimethyl disulfide was added (a sulfur content of 3% by mass) was used, and the catalyst layer average temperature was 300 ° C., the hydrogen partial pressure was 6 MPa, the liquid space velocity was 1 h ⁻¹ , hydrogen / oil. The catalyst was presulfided for 4 hours under the condition of a ratio of 200 NL / L. For catalyst B, reduction was performed for 6 hours under the conditions of an average catalyst layer temperature of 320 ° C., a hydrogen pressure of 5 MPa, and a hydrogen gas amount of 83 ml / min. Processed.

After preliminary sulfidation and reduction treatment, the sulfur content of the mixed oil (in terms of sulfur atoms) is added to the mixed oil (40% by mass of palm oil) and 60% by mass of palm kernel oil (the fatty acid composition of the mixed oil is shown in Table 2). ) Was adjusted to 10 mass ppm by adding dimethyl sulfide to adjust the oil to be treated. Thereafter, hydrotreating and isomerization were performed using the oil to be treated. The hydrorefining conditions were a reaction temperature (catalyst layer average temperature) of 300 ° C., a hydrogen pressure of 5 MPa, a liquid space velocity of 0.5 h ⁻¹ , and a hydrogen / oil ratio of 500 NL / L. The treated oil after the hydrotreatment was introduced into a high pressure separator, and hydrogen, hydrogen sulfide, carbon dioxide and water were removed from the treated oil. The spilled oil obtained from the high pressure separator is in the second reaction tube, the reaction temperature (catalyst layer average temperature) is 300 ° C., the hydrogen pressure is 3 MPa, the liquid space velocity is 1 h ⁻¹ , and the hydrogen / oil ratio is 500 NL / L. As a result, hydroisomerization treatment was performed. The oil after the hydroisomerization treatment was further guided to a rectification column, and fractionated into a light fraction having a boiling point range of less than 140 ° C, an intermediate fraction having a boiling point of 140 to 300 ° C, and a heavy fraction having a temperature exceeding 300 ° C. The fraction at 140 to 300 ° C. was used as the aviation fuel oil base material 1. Table 3 shows the yield and precipitation point of the aviation fuel base material 1.
The aviation fuel oil base yield is the mass ratio of the 140-300 ° C. fraction with respect to the total amount of hydroisomerized oil obtained by hydrotreating and hydroisomerizing the feedstock oil. The precipitation point means a value measured according to JIS K2276 “Petroleum products—Aeronautical fuel oil test method—Precipitation point test method”.

(Example 2)
The aviation fuel oil base material 2 was obtained in the same manner as in Example 1 except that a mixed oil of 45% by mass of palm oil, 15% by mass of soybean oil and 40% by mass of coconut oil was used. Table 3 shows the yield and precipitation point of the obtained aviation fuel base material 2.

(Example 3)
The aviation fuel oil base 3 was treated in the same manner as in Example 1 except that a mixed oil of 30% by mass of soybean oil, 50% by mass of palm kernel oil, and 20% by mass of coconut oil was treated under the treatment conditions shown in Table 3. Obtained. Table 3 shows the yield and precipitation point of the obtained aviation fuel base material 3.

(Comparative Example 1)
A comparative aviation fuel oil base material 1 was obtained in the same manner as in Example 1 except that 100% by mass of palm oil was used and the treatment was performed under the treatment conditions shown in Table 3. Table 3 shows the yield and precipitation point of the obtained comparative aviation fuel base material 1.

(Comparative Example 2)
A comparative aviation fuel oil base material 1 was obtained in the same manner as in Example 1 except that 100% by mass of soybean oil was used and treated under the treatment conditions shown in Table 3. Table 3 shows the yield and precipitation point of the obtained comparative aviation fuel base material 2.

  As shown in Table 3, in Examples 1 to 3, compared with Comparative Examples 1 and 2, an aviation fuel oil base material having a high base material yield, a low precipitation point and excellent low temperature performance was obtained.

  INDUSTRIAL APPLICABILITY The present invention provides a method for producing an aviation fuel oil base material derived from animal and vegetable oils having a high base material yield and excellent low temperature performance.

Claims (3)

  A first step of hydrotreating a mixture of two or more animal and vegetable oils and fats having different fatty acid compositions and a sulfur-containing hydrocarbon compound in the presence of hydrogen, and hydrogen obtained in the first step A second step of hydroisomerizing the hydrotreated oil in the presence of hydrogen, and in the mixture of animal and vegetable oils and fats, the total amount of each fatty acid composition having a fatty acid carbon chain having 9 to 15 carbon atoms is 50 to The ratio of each fatty acid composition having carbon number 11, carbon number 13 and carbon number 15 fatty acid carbon chain is 70% by mass and the total amount of fatty acid composition having 9 to 15 carbon atoms is 100. The manufacturing method of the aviation fuel oil base material characterized by being 10-60. In the first step, a mixture of two or more animal and vegetable oils and fats having different fatty acid compositions in the presence of hydrogen, and a raw material oil containing a sulfur-containing hydrocarbon compound, aluminum, silicon, zirconium, boron, titanium and magnesium A porous inorganic oxide comprising two or more elements selected from the group consisting of elements selected from the group 6A and group 8 elements of the periodic table supported by the porous inorganic oxide; The raw material oil is hydrogenated under the conditions of a hydrogen pressure of 2 to 13 MPa, a liquid space velocity of 0.1 to 3.0 h ⁻¹ , a hydrogen / oil ratio of 150 to 1500 NL / L, and a reaction temperature of 150 to 480 ° C. using the contained catalyst. The aviation fuel oil base material according to claim 1, comprising a step of removing hydrogen, hydrogen sulfide, carbon dioxide, and water from the treatment object obtained to obtain a hydrotreated oil. Made Method. In the second step, the hydrotreated oil obtained in the first step is further made of a substance selected from aluminum, silicon, zirconium, boron, titanium, magnesium and zeolite in the presence of hydrogen. Using a catalyst formed by supporting a metal selected from Group 8 elements of a periodic table on a support made of a conductive inorganic oxide, a hydrogen pressure of 2 to 10 MPa, a liquid space velocity of 0.1 to 3.0 h ⁻¹ , hydrogen / The method for producing an aviation fuel base material according to claim 1 or 2, wherein the hydroisomerization process is performed under conditions of an oil ratio of 100 to 1500 NL / L and a reaction temperature of 250 to 330 ° C. .