JP5091762B2 - Gas oil base and gas oil composition - Google Patents

Description

  The present invention relates to a light oil base and a light oil composition.

  Conventionally, as a base material for diesel oil, straight run diesel oil obtained from crude oil atmospheric distillation equipment has been hydrorefined and hydrodesulfurized, and hydrogenated to straight run kerosene obtained from crude oil atmospheric distillation equipment. Those subjected to purification and hydrodesulfurization are known. A conventional light oil composition is produced by blending one or more of the above light oil base and kerosene base. Moreover, additives, such as a cetane number improver and a detergent, are mix | blended with these light oil compositions as needed (for example, refer nonpatent literature 1).

By the way, in recent years, reduction of sulfur content and aromatic content in light oil, which is a fuel for internal combustion engines, has been demanded with the aim of promptly improving the air environment and reducing the environmental load. At the same time, in order to cope with the global warming problem, there is a demand for fuel properties that contribute to further improvement in fuel efficiency and reduce carbon dioxide (CO ₂ ). Synthetic fuels and renewable energy are one of the solutions. The use of biodiesel fuel, which is energy (hereinafter also referred to as “BDF”), as an alternative fuel is being studied.

  BDF is mainly a mixture of fatty acid alkyl esters made from natural animal and plant oils and fats. Influence of poisoning on aromatic compounds and exhaust gas aftertreatment catalysts that are considered to have a large contribution to soot formation in exhaust gas Since it is an oxygen-containing compound that has almost no sulfur content and has oxygen in the molecule, it has attracted attention as a promising candidate for alternative fuels. In addition, because it is plant-derived, it is positioned as a renewable energy, so the international carbon dioxide reduction protocol signed in 1997, the so-called Kyoto Protocol, does not count carbon dioxide derived from BDF as an emission amount. The BDF also has a policy merit.

  For example, Patent Document 1 has been activated with natural fats and oils, waste natural fats or derivatives thereof for the purpose of providing a method for producing hydrocarbons using natural fats or derivatives thereof and edible waste oils as raw materials. There has been disclosed a method for producing hydrocarbons characterized by reacting hydrogen with a catalyst selected from the group consisting of a metal catalyst, an alloy catalyst, a metal-supported catalyst and an alloy-supported catalyst.

  In addition, Patent Document 2 discloses that a component or a mixture of components prepared from biological raw materials originating from plants and / or animals and / or fish is 0.1 to 99% by volume and a component containing oxygen is 0 to A diesel engine fuel composition containing 20% by volume is disclosed. Both components are said to be mixed with diesel components based on crude oil and / or fractions from the Fischer-Tropsch process.

Patent Document 3 discloses an environment-friendly diesel fuel composition comprising a methyl ester or ethyl ester of a saturated or unsaturated fatty acid having 6 to 20 carbon atoms constituting a fatty acid, or a mixture thereof. .
JP 2003-171670 A JP 2005-538204 A JP 2004-189885 A Seiichi Konishi, “Introduction to Fuel Engineering”, Saika Hanafusa, March 1991, p. 136-144

  However, fatty acid alkyl esters using natural animal and vegetable oils and fats as raw materials are inherently heavy, and there is a concern that unburned hydrocarbon emissions during combustion may increase due to poor burn-off in engine combustion and the like. In addition, since fatty acid alkyl esters are oxygen-containing compounds, there is a concern of increasing the emission of aldehydes during combustion. In the case of BDF containing many fatty acid alkyl esters having many saturated fatty acid groups, since it is solid at room temperature, it is inferior in handling as a fuel, and it is difficult to ensure fluidity at low temperatures. In the case of BDF containing a lot of unsaturated fatty acid groups, its chemical composition is inferior in oxidative stability, and there is concern about deterioration of hue, generation of sludge, and adverse effects on engine members. Furthermore, the fatty acid glyceride, the alkyl alcohol, and the glycerin mixture, which is a by-product, are raw materials used for refining the fatty acid alkyl ester, which are extremely concerned about adverse effects on engine members and fuel injection systems.

  These tendencies have not been observed in conventional general light oils and the like. Therefore, not only when using BDF alone but also when mixing with existing light oils and the like, the same problem occurs. In addition to paying attention to the properties of BDF itself, it is necessary to pay more attention to oxidation stability, low-temperature performance, combustibility, etc. than before even when mixed with light oil other than BDF.

Therefore, the conventional fatty acid alkyl ester mixture made from natural animal and vegetable oils and fats is provided for providing a light oil composition that has excellent life cycle CO ₂ emission characteristics and oxidation stability as well as reduction of harmful exhaust components, and good low-temperature performance. Using BDF, these performance improvements cannot be achieved simultaneously. Furthermore, because these engine performances are closely related to other fuel properties, it is very difficult to design high-quality fuels that can simultaneously achieve these required performances at a high level, and are required as commercial fuel oils. There are no examples or knowledge based on the examination of practical manufacturing methods that satisfy the various performances.

The present invention has been made in view of such a situation, and the object thereof is life cycle CO ₂ emission characteristics and oxidation stability obtained using a raw material containing an oxygen-containing hydrocarbon compound derived from animal and vegetable oils, An object of the present invention is to provide a light oil base material and a light oil composition excellent in low temperature fluidity.

In order to solve the above-described problems, the present invention hydrotreats an oil to be treated containing oxygen-containing hydrocarbon compounds, aliphatic hydrocarbon compounds, and sulfur-containing hydrocarbon compounds derived from animal and vegetable oils in the presence of hydrogen. And the content of normal paraffin is 90% by mass or more, and the specified carbon number n in the hydrocarbon fraction (10 ≦ n ≦ 20; n indicates an even number). _{a n} total paraffin content of (unit: mass%), _B the total paraffin content in the carbon number of _n-1 n-1 (unit: mass%), the ratio of _{B n-1} with respect to _{a n (B n −1} / A _n ), the average value of (B _n-1 / A _n ) in 10 ≦ n ≦ 20 is 0.30 or more.

  Here, if the said to-be-processed oil is hydrotreated, the hydrodeoxygenation reaction of the oxygen-containing hydrocarbon compound originating in animal and vegetable oil will advance, and a hydrocarbon will produce | generate. The “hydrodeoxygenation reaction” in the present invention means a reaction in which oxygen atoms constituting the oxygen-containing hydrocarbon compound are removed and hydrogen is added to the cleaved portion. For example, fatty acid triglycerides and fatty acids have oxygen-containing groups such as ester groups and carboxyl groups, respectively, but oxygen atoms contained in these oxygen-containing groups are removed by hydrodeoxygenation reaction, and oxygen-containing hydrocarbons. The compound is converted to a hydrocarbon. There are mainly two reaction pathways for hydrodeoxygenation of oxygen-containing groups of fatty acid triglycerides and the like. The first reaction pathway is a decarboxylation pathway in which oxygen-containing groups such as fatty acid triglycerides are eliminated as carbon dioxide as they are, and oxygen atoms are removed as carbon dioxide. The second reaction route is a hydrogenation route that is reduced via an aldehyde or alcohol while maintaining the number of carbon atoms such as fatty acid triglyceride. In this case, oxygen atoms are converted to water. When these reactions proceed in parallel, hydrocarbons, water, and carbon dioxide are generated.

A reaction scheme of hydrodeoxygenation taking the case of an alkyl ester of stearic acid as an example is shown in the following formulas (1) and (2). The reaction scheme represented by the formula (1) corresponds to the first reaction path, and the reaction scheme represented by the formula (2) corresponds to the second reaction path. In the formulas (1) and (2), R represents an alkyl group.
C ₁₇ H ₃₅ COOR + H ₂ → C ₁₇ H ₃₆ + CO ₂ + RH (1)
_{C 17 H 35 COOR + 4H 2} → C 18 H 38 + 2H 2 O + RH (2)

  In addition, although the normal carbon number n in a hydrocarbon fraction is an even number in the range of 10 to 20, this is because the carbon number of the oxygen-containing hydrocarbon compound derived from animals and plants is usually an even number. In addition, the normal paraffin content and the total paraffin content in the present invention mean values (unit: mass%) measured using a gas chromatograph / time-of-flight mass spectrometer (GC-TOFMS). In GC-TOFMS, first, constituent components of a sample are separated by gas chromatography, and each separated component is ionized. Next, the ions are mass-separated based on the flight speed when a constant acceleration voltage is applied to the ions depending on the mass of the ions, and a mass spectrum is obtained based on the difference in arrival time to the ion detector. The amount of paraffin may be obtained directly from the mass spectrum, but based on the mass spectrum data, create a graph showing the correlation between the retention time and the intensity of gas chromatography for each component having the same carbon number, You may obtain | require the said paraffin amount from the peak area ratio of each component in the graph.

That, B _{n-1 /} A _n in the present invention is an index correlated with the ratio of the two reaction paths in hydrodeoxygenation reactions of oxygenated hydrocarbon compounds n carbon atoms. Further, the average value of the oxygenated 10 ≦ n ≦ 20 with carbon number _{n (B n-1 / A} n) is 0.30 or _{more, B 9 / A 10, B} 11 / A 12, B 13 It means that the average value of / A ₁₄ , B ₁₅ / A ₁₆ , B ₁₇ / A ₁₈ and B ₁₉ / A ₂₀ is 0.30 or more. In addition, when the numerical value does not exist in either one or both of the total paraffin amount A _n and B _n−1 at the defined carbon number n of the hydrocarbon fraction (the value of the total paraffin amount is 0), (B _{n −1} / A _n ) is not calculated, and is not taken into account in the average value of (B _n−1 / A _n ).

  Moreover, the aliphatic hydrocarbon compound contained in the to-be-processed oil has the role which suppresses the temperature rise by the heat of reaction in hydroprocessing. On the other hand, the sulfur-containing hydrocarbon compound contained in the oil to be treated has a role of improving the deoxygenation activity in the hydrotreatment.

According to the light oil base material of the present invention, it is possible to achieve all of life cycle CO ₂ emission characteristics, oxidation stability, and low temperature fluidity in a sufficient and balanced manner by having the above configuration.

  Further, in the conventional light oil base material production method, hydroisomerization is generally performed in view of the technical level in the field that normal paraffin hydroisomerization is generally performed for the purpose of improving low-temperature characteristics. It can be said that it is an unexpected remarkable effect that the above-mentioned excellent effect is obtained by the light oil base material of the present invention in which the content of normal paraffin is 90% by mass or more, which is obtained without going through.

  In the present invention, the oxygen-containing hydrocarbon compound derived from animal and vegetable oils is preferably one or more compounds selected from fatty acids and fatty acid esters, and the fatty acid esters are more preferably triglycerides of fatty acids.

  Moreover, as the aliphatic hydrocarbon compound, a recycled oil obtained by recycling the hydrocarbon fraction obtained by hydrotreating the oil to be treated in advance can be preferably used. In this case, the recycle ratio (mass ratio of recycle oil to oxygenated hydrocarbon compound) is preferably 0.5 to 5 times.

  The present invention also includes a light oil base material containing 10% by volume or more of the light oil base material of the present invention, and a low-temperature fluidity improver of 10 to 1000 ppm by mass based on the total amount of the light oil composition, 90 % Distillation temperature of 360 ° C. or less, sulfur content of 10 mass ppm or less, oxygen content of 1 mass% or less, fatty acid alkyl ester content of 3.5 mass% or less, acid value of 0.13 mg KOH / g or less, methanol content of 0.01 mass A gas oil composition characterized by having a glyceride content of 0.01% by mass or less and a clogging point of −5 ° C. or less is provided.

As described above, according to the present invention, a light oil base material excellent in life cycle CO ₂ emission characteristics, oxidation stability, and low-temperature fluidity obtained by using a raw material containing an oxygen-containing hydrocarbon compound derived from animal and vegetable oils. And a light oil composition can be provided.

  Hereinafter, preferred embodiments of the present invention will be described in detail.

  In the present invention, an oil to be treated containing an oxygen-containing hydrocarbon compound, an aliphatic hydrocarbon compound, and a sulfur-containing hydrocarbon compound derived from animal and vegetable oils is used. As substances derived from animal and vegetable oils, oil and fat components derived from animal and vegetable oils and derivatives thereof are preferable because hydrodecarboxylation reaction easily occurs. Here, the oil and fat component maintains and improves the performance of natural and artificially produced and manufactured animal and vegetable oils and animal and vegetable oil components and / or components derived and produced from these oils and fats and these oil and fat products. The component added for the purpose of making it included is included. In addition, the derivative of the fat and oil component includes a component by-produced in the process of producing the fat and oil product and a component intentionally converted into the derivative.

  Examples of fat components derived from animal and vegetable oils include beef tallow, rapeseed oil, soybean oil, palm oil, corn oil and the like. In the present invention, any fats and oils derived from animal and vegetable oils may be used, and waste oil after using these fats and oils may be used. However, vegetable oils and fats are preferable from the viewpoint of carbon neutral, and rapeseed oil, soybean oil, and palm oil are more preferable from the viewpoint of the number of fatty acid alkyl chain carbons and their reactivity. In addition, you may use said fats and oils individually by 1 type or in mixture of 2 or more types.

Derivatives of fat and oil components derived from animal and vegetable oils may include components processed into ester bodies such as fatty acids constituting the fatty acid triglycerides of the fat and oil components and methyl esters thereof. Typical examples of fatty acids constituting these fatty acid triglycerides include butyric acid (C ₃ H ₇ COOH) and caproic acid (C ₅ H ₁₁ COOH), which are fatty acids having no unsaturated bond in the molecular structure called saturated fatty acid. , 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), linoleic acid (C ₁₇ H ₃₁ COOH), linolenic acid (C), which are unsaturated fatty acids having one or more unsaturated bonds ₁₇ H ₂₉ COOH), ricinolenic acid (C ₁₇ H ₃₂ (OH) COOH) and the like.

  The aliphatic hydrocarbon compound contained in the oil to be treated has a role of suppressing a temperature rise due to reaction heat in the hydrotreatment. The aliphatic hydrocarbon compound may be linear, branched or cyclic, or a mixture thereof. Moreover, the fraction obtained by the hydrocarbon fraction obtained by the hydrogenation process mentioned later containing these components, a petroleum refinery process, and a chemical manufacturing process may be sufficient. In particular, in the present invention, treated oil from which unreacted raw materials, light gas fractions and heavy by-products have been removed from the distillate obtained by hydrotreating, or the treated oil is fractionated in a rectifying column. Since it is easy to obtain the hydrocarbon fraction obtained in this way, it is preferable to recycle a part of these to the oil to be treated. The boiling range of the hydrocarbon fraction obtained by fractional distillation in the rectification column is preferably 150 to 350 ° C.

  The ratio of the oxygen-containing hydrocarbon compound and the aliphatic hydrocarbon compound derived from the animal and vegetable oil is not particularly limited. For example, if the specific heat of both is the same, the temperature increase is derived from the animal and vegetable oil if the mixture is one-to-one. Since it becomes half of the case of reacting the oxygen-containing hydrocarbon compound alone, the ratio may be determined according to the maximum operating temperature of the reactor. However, when the ratio of the aliphatic hydrocarbon compound is increased, the concentration of the oxygen-containing hydrocarbon compound derived from the animal and vegetable oil is decreased and the reactivity is decreased, and the flow rate of the piping is increased, resulting in a large load. The amount of the aliphatic hydrocarbon compound with respect to the oxygen-containing hydrocarbon compound derived from animal or vegetable oil is preferably 5 times by mass or less.

  Furthermore, it is possible to connect a plurality of reactors in series and add an additional aliphatic hydrocarbon compound between the reactors.

  The sulfur-containing hydrocarbon compound contained in the oil to be treated is not particularly limited, and specific examples include sulfides, disulfides, polysulfides, thiols, thiophenes, benzothiophenes, dibenzothiophenes, and derivatives thereof. The sulfur-containing hydrocarbon compound contained in the oil to be treated may be a single compound or a mixture of two or more. Furthermore, a petroleum hydrocarbon fraction containing a sulfur content may be mixed with the oil to be treated.

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

  The sulfur content contained in the oil to be treated is preferably 1 to 50 ppm by mass, preferably 5 to 30 ppm by mass, in terms of sulfur atom, with respect to the oxygen-containing hydrocarbon compound derived from animal and vegetable oils and fats. Is 10-20 ppm by mass. 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, if it exceeds 50 ppm by mass, the sulfur content in the light gas discharged in the hydrorefining process will increase, and the sulfur content in the hydrorefined oil will tend to increase. When used as a fuel such as, there is a concern about the adverse effect on the engine exhaust gas purification device. 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.

  The sulfur-containing hydrocarbon compound may be premixed with the oil to be treated and the mixture introduced into the reactor of the hydrotreating apparatus, or when the oil to be treated is introduced into the reactor, You may supply.

  In the hydrogenation treatment 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 oxide are supported. A catalyst containing one or more metals selected from Group 6A and Group 8 elements of the periodic table is preferably used.

  As the catalyst support used in the present invention, as described above, a porous inorganic oxide comprising at least two selected from aluminum, silicon, zirconium, boron, titanium and magnesium is preferably used. The porous inorganic oxide is more preferably 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. Inorganic oxides containing elements (complex oxides of aluminum oxide and other oxides) are more preferable.

  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 hydrotreated 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 support preferably 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, if it exceeds 35% by mass, the metal is not effectively dispersed and sufficient activity tends not to be 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 type and combination of the catalysts used for the hydrotreatment are 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.

  When a plurality of catalysts having different support components are combined, 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.

  In the present invention, one of the above catalysts may be used alone, or a plurality of catalysts having different active metal species and carrier constituent components may be used in combination. Suitable combinations when using a plurality of types of catalysts include, for example, a catalyst containing cobalt-molybdenum after the catalyst containing nickel-molybdenum, and a nickel-cobalt-molybdenum after the catalyst containing nickel-molybdenum. A catalyst containing nickel-tungsten, 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.

  Furthermore, in addition to the above catalyst (hydrotreating catalyst), for the purpose of trapping the scale component that flows along with the oil to be treated, if necessary, or supporting the hydrotreating catalyst at the separation part of the catalyst bed. A guard catalyst, a metal removal catalyst, or an inert packing may be used. In addition, these can be used individually or in combination.

The conditions for contacting the oil to be treated and the catalyst in the presence of hydrogen are a hydrogen pressure of 1 to 6 MPa and a liquid space velocity (LHSV) of 0.1 to 0.7 h ⁻¹ , preferably a hydrogen pressure. It is more preferable that they are 2-4 Mpa and liquid space velocity 0.2-0.5h- ¹ . When the hydrogen pressure is 6 MPa or more, the ratio between the decarboxylation reaction and the hydrogenation reaction is constant. When the hydrogen pressure is less than 6 MPa, the decarboxylation ratio increases as the pressure decreases, and the effect of suppressing the amount of heat generated by the reaction appears. To do. However, when the hydrogen pressure is less than 1 MPa, the reactivity tends to decrease or the activity tends to decrease rapidly. On the other hand, when the liquid space velocity is 0.7 h ⁻¹ or more, the ratio of the decarboxylation reaction and the hydrogenation reaction is constant, but when it is less than 0.7 h ⁻¹ , the decarboxylation ratio increases as the space velocity decreases. And the effect of suppressing the calorific value by reaction appears. However, if the amount is less than the above lower limit value, a reactor having an extremely large internal volume is required, and excessive capital investment tends to be required.

  The hydrogen oil ratio (hydrogen / oil ratio) in the hydrotreatment is preferably in the range of 100 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 under the above hydrogen pressure and liquid space velocity conditions is inhibited, and when it falls below the above lower limit, there is a possibility that sufficient hydrogenation reaction does not proceed. is there.

  The reaction temperature in the hydrotreatment is preferably in the range of 180 to 390 ° 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 180 ° C., sufficient hydrogenation reaction does not proceed, and when it is higher than 390 ° 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 parallel flow type with respect to the oil to be treated. 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 hydrotreated oil hydrotreated in the reactor is fractionated into a hydrotreated oil containing a predetermined fraction through a gas-liquid separation process, a rectification process, and the like. For example, it is fractionated into a light oil fraction and a residual fraction. Furthermore, the gas, naphtha fraction, and kerosene fraction may be fractionated as necessary. 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 addition, water, carbon monoxide, carbon dioxide, hydrogen sulfide, etc. may be generated due to the reaction of oxygen and sulfur contained in the oil to be treated. A gas-liquid separation facility or other by-product gas removal device may be installed in the recovery process.

  In general, hydrogen gas is introduced from the inlet of the first reactor along with the oil to be treated before or after passing through the heating furnace, but separately from this, the temperature in the reactor is controlled. In order to maintain the hydrogen pressure throughout the reactor, hydrogen gas may be introduced between the catalyst beds or between a plurality of reactors. The hydrogen thus introduced is generally called quench hydrogen. The ratio of quench hydrogen to hydrogen gas introduced along with the oil to be treated 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.

The light oil base material of the present invention is a hydrocarbon fraction obtained by the hydrogenation treatment as described above, wherein the content of normal paraffin is 90% by mass or more, and the specified carbon number n ( 10 ≦ n ≦ 20; n is an even number.) The total paraffin content in A _n (unit: mass%), the total paraffin content in carbon number n−1 is B _n-1 (unit: mass%), when the ratio of _{B n-1} with respect to a _n and _{(B n-1 / a n} ), the mean value of the _{10 ≦ n ≦ 20 (B n} -1 / a n) is of 0.30 or more .

  In addition, when content of normal paraffin falls, the cetane number of a light oil base material may fall, and there exists a possibility of raising a concern about the practical performance when it makes a light oil product.

Moreover, the average value of ( _Bn-1 / _An ) in 10 <= n <= 20 is 0.30 or more, Preferably it is 0.40 or more, More preferably, it is 0.50 or more. When the average value is less than 0.30, the low temperature performance of the base material itself is deteriorated due to the distortion of the paraffin distribution in the environmental low load type environmental base material, and the low temperature in the light oil composition when the base material is used. The effect of adding a fluidity improver deteriorates.

  Further, the light oil composition of the present invention contains a light oil base material containing 10% by volume or more of the light oil base material of the present invention, and a low temperature fluidity improver of 10 to 1000 mass ppm based on the total amount of the light oil composition. 90% distillation temperature of 360 ° C. or less, sulfur content of 10 mass ppm or less, oxygen content of 1 mass% or less, fatty acid alkyl ester content of 3.5 mass% or less, acid value of 0.13 mg KOH / g or less, methanol content of 0 It satisfies the requirements of 0.01 mass% or less, a glyceride content of 0.01 mass% or less, and a clogging point of −5 ° C. or less.

  The light oil composition of the present invention may contain a base other than the light oil base of the present invention as long as the properties of the intended light oil composition are obtained. Such base materials include straight-run lamps and light oil fractions obtained from a crude oil atmospheric distillation device, straight-run heavy oil obtained from an atmospheric distillation device, and residual oil obtained by treating with a vacuum distillation device. Catalytic cracking lamps / light oil fractions, hydrocracking lamps / light oil fractions obtained by catalytic cracking or hydrocracking of kerosene / light oil fractions, decompressed heavy gas oils or desulfurized heavy oils, and hydrogenating these petroleum hydrocarbons Hydrorefining lamp / light oil fraction obtained by refining, hydrodesulfurization lamp / light oil fraction, etc., and synthetic light / light oil fraction synthesized from natural gas, asphalt, coal, biomass, etc. Can be preferably used. In the light oil composition of the present invention, a plurality of these kerosene / light oil fraction base materials and kerosene fraction base materials may be blended in a category that satisfies a predetermined condition.

  The clogging point (CFPP) of the light oil composition of the present invention needs to satisfy −5 ° C. or less which is JIS No. 2 light oil standard. Furthermore, it is preferably −6 ° C. or lower, more preferably −7 ° C. or lower, from the viewpoint of preventing the prefilter blockage of the diesel vehicle. Here, the clogging point refers to a clogging point measured according to JIS K 2288 “Light oil—clogging point test method”.

  The sulfur content of the light oil composition of the present invention needs to be 10 mass ppm or less from the viewpoint of reducing harmful exhaust components discharged from the engine and improving the performance of the exhaust gas aftertreatment device, preferably 5 mass ppm or less, More preferably, it is 3 mass ppm or less, More preferably, it is 1 mass ppm or less. In addition, the sulfur content here means the mass content of the sulfur content based on the total amount of the light oil composition measured by JIS K2541 “Sulfur content test method”.

The oxygen content of the light oil composition of the present invention is required to be 1% by mass or less, preferably 0.8% by mass or less, more preferably 0.6% by mass or less, from the viewpoint of improving oxidation stability. Preferably it is 0.4 mass% or less, Most preferably, it is 0.2 mass% or less. The oxygen content can be measured with a general elemental analyzer. For example, the sample is converted to CO on platinum carbon, or further converted to CO ₂ and then measured using a thermal conductivity detector. You can also.

  The flash point of the light oil composition of the present invention is preferably 45 ° C. or higher. When the flash point is less than 45 ° C., it cannot be handled as a light oil composition for safety reasons. For the same reason, the flash point is preferably 54 ° C. or higher, more preferably 58 ° C. or higher. In addition, the flash point as used in the field of this invention shows the value measured by JISK2265 "Crude oil and petroleum product flash point test method".

  The cetane index of the light oil composition of the present invention is preferably 45 or more. When the cetane index is less than 45, the concentration of PM, aldehydes, or NOx in the exhaust gas tends to increase. For the same reason, the cetane index is preferably 48 or more, and most preferably 51 or more. The cetane index referred to in the present invention is defined by “Calculation method of cetane index using 8.4 variable equations” in JIS K 2280 “Petroleum products-fuel oil-octane number and cetane number test method and cetane index calculation method”. It means the calculated value. Here, the cetane index in the JIS standard is generally applied to light oil to which a cetane number improver is not added, but in the present invention, the above-mentioned " Applying “8.4 Calculation Method of Cetane Index Using Variable Equation”, a value calculated by the calculation method is expressed as a cetane index.

Density at 15 ℃ of the gas oil composition of the present invention, in terms of calorific value ensuring, is preferably 750 kg / ^{m 3} or more, more preferably 760 kg / ^{m 3} or more, more preferably 770 kg / ^{m 3} or more. Further, the density, NOx, from the viewpoint of reducing the emission of PM, it is preferably 850 kg / ^{m 3} or less, more preferably 845 kg / ^{m 3} or less, more preferably 840 kg / ^{m 3} or less. In addition, the density here means the density measured by JIS K 2249 “Density test method and density / mass / capacity conversion table of crude oil and petroleum products”.

  The light oil composition of the present invention desirably has a lubricating performance such that the HFRR wear scar diameter (WS1.4) is preferably 460 μm or less, more preferably 430 μm or less, and even more preferably 410 μm or less. When the HFRR wear scar diameter (WS1.4) exceeds 460 μm, especially in a diesel engine equipped with a distribution type injection pump, it causes an increase in driving torque of the pump during operation and an increase in wear of each part of the pump. The engine itself may be destroyed as well as the performance deterioration. In addition, in an electronically controlled fuel injection pump capable of high-pressure injection, there is a concern about wear on the sliding surface. The HFRR wear scar diameter (WS1.4) as used in the present invention is a value measured by the Petroleum Institute Standard JPI-5S-50-98 “Light Oil-Lubricity Test Method” issued by the Japan Petroleum Institute. Means.

  Although there is no restriction | limiting in particular in the aromatic content in the light oil composition of this invention, it is preferable that it is 20 volume% or less from a viewpoint of improving an environmental impact reduction effect and NOx and PM reduction, More preferably, it is 19 volume% or less. More preferably, it is 18 volume% or less. The aromatic content in the present invention was measured in accordance with the Petroleum Institute Method JPI-5S-49-97 “Hydrocarbon Type Test Method—High Performance Liquid Chromatograph Method” published by the Japan Petroleum Institute. It means the volume percentage (volume%) of aromatic content.

  The water content of the light oil composition of the present invention is preferably 300 ppm by volume or less, more preferably 250 ppm by volume or less, from the viewpoint of adverse effects on members to fuel tanks and the like and suppression of hydrolysis of ester compounds. Preferably, it is 200 volume ppm or less. In addition, the water | moisture content here is the water prescribed | regulated by JISK2275 "moisture test method (crude oil and petroleum products)."

  As a distillation property in the light oil composition of the present invention, the 90% distillation temperature needs to be 360 ° C. or less, preferably 340 ° C. or less, more preferably 330 ° C. or less, and further preferably 320 ° C. or less. . When the 90% distillation temperature exceeds 360 ° C., the amount of PM and fine particles discharged tends to increase. The 90% distillation temperature is preferably 280 ° C. or higher, more preferably 285 ° C. or higher, further preferably 290 ° C. or higher, and even more preferably 295 ° C. or higher. If the 90% distillation temperature is less than 280 ° C., the fuel efficiency improvement effect becomes insufficient and the engine output tends to decrease. The 90% distillation temperature here means a value measured according to JIS K 2254 “Petroleum products—Distillation test method—Normal pressure method”.

The kinematic viscosity at 30 ° C. of the light oil composition of the present invention is not particularly limited, but is preferably 2.5 mm ² / s or more, more preferably 2.7 mm ² / s or more, and 2.9 mm ^2. / S or more is more preferable. If the kinematic viscosity is less than 2.5 mm ² / s, it tends to be difficult to control the fuel injection timing on the fuel injection pump side, and the lubricity of each part of the fuel injection pump mounted on the engine is impaired. There is a fear. Moreover, kinematic viscosity at 30 ° C. of the gas oil composition of the present invention is preferably at most ^{5 mm} 2 / s, more preferably not more than 4.7 mm ² / s, or less 4.5 mm ² / s Is more preferable. If the kinematic viscosity exceeds 5 mm ² / s, the resistance inside the fuel injection system increases, the injection system becomes unstable, and the concentrations of NOx and PM in the exhaust gas increase. In addition, kinematic viscosity here means kinematic viscosity measured by JISK2283 "crude oil and petroleum products-kinematic viscosity test method and viscosity index calculation method".

  In the light oil composition of the present invention, the acid value is required to be 0.13 mgKOH / g or less from the viewpoint of adverse effects on engine members. Since the acid value indicates the amount of free fatty acid in the mixture, if this value is large, there is a concern that the acidic compound may adversely affect the member. Therefore, the acid value is preferably 0.10 mgKOH / g or less, more preferably 0.08 mgKOH / g or less, and further preferably 0.05 mgKOH / g or less. In addition, an acid value here means the acid value measured by JISK2501 "Petroleum products and lubricating oil-neutralization number test method".

  In the light oil composition of the present invention, the fatty acid methyl ester content is required to be 3.5% by mass or less from the viewpoint of deterioration of burnout in engine combustion or the like. Preferably it is 2.0 mass% or less, More preferably, it is 1.0 mass% or less, More preferably, it is 0.5 mass% or less. Here, the fatty acid methyl ester content means the fatty acid methyl ester content measured according to EN 14103.

  In the light oil composition of the present invention, the methanol content must be 0.01% by mass or less from the viewpoint of adverse effects on the fuel injection system. Preferably it is 0.008 mass% or less, More preferably, it is 0.006 mass% or less, More preferably, it is 0.005 mass% or less. The methanol content here means a methanol content measured according to JIS K 2536 and EN 14110.

  In the light oil composition of the present invention, the glyceride content must be 0.01% by mass or less from the viewpoint of adverse effects on the fuel injection system. Preferably it is 0.008 mass% or less, More preferably, it is 0.006 mass% or less, More preferably, it is 0.005 mass% or less. The glyceride content here means a glyceride content measured in accordance with EN 14105.

  The above mixed oil is blended with a low temperature fluidity improver in order to improve low temperature performance. The type of low-temperature fluidity improver is not particularly limited, but linear compounds such as ethylene-unsaturated ester copolymers represented by ethylene-vinyl acetate copolymers, alkenyl succinic acid amides, and dibehenate esters of polyethylene glycol. , Low temperature fluidity improvers such as comb polymers composed of alkyl fumarate or alkyl itaconate-unsaturated ester copolymers, acids such as phthalic acid, succinic acid, ethylenediaminetetraacetic acid, nitriloacetic acid, or acid anhydrides thereof, etc. And a low-temperature fluidity improver containing a polar nitrogen compound consisting of a reaction product of hydrocarbyl-substituted amine and the like, and one or more of these compounds may be used in combination. Among these, from the viewpoint of versatility, an ethylene-vinyl acetate copolymer additive and a low-temperature fluidity improver containing a polar nitrogen compound can be preferably used to prevent wax crystal refinement and prevent wax aggregation and sedimentation. Therefore, it is more preferable to use a low temperature fluidity improver containing a polar nitrogen compound.

  The content of the low temperature fluidity improver is 10 to 1000 mg / L, preferably 50 to 500 mg / L, more preferably 100 to 300 mg / L, based on the total amount of the composition. If the content of the low temperature fluidity improver is less than the lower limit, the effect of improving the low temperature fluidity due to the addition tends to be insufficient. Moreover, even if content of a low temperature fluidity improver exceeds the said upper limit, the further improvement effect of the low temperature fluidity commensurate with content is not acquired.

  In the light oil composition of the present invention, if necessary, an appropriate amount of a cetane number improver can be blended to improve the cetane number of the resulting light oil composition. As the cetane number improver, various compounds known as light oil cetane number improvers can be arbitrarily used, and examples thereof include nitrate esters and organic peroxides. These cetane number improvers may be used alone or in combination of two or more.

  In the present invention, it is preferable to use a nitrate ester among the cetane number improvers described above. Such nitrate esters include 2-chloroethyl nitrate, 2-ethoxyethyl nitrate, isopropyl nitrate, butyl nitrate, primary amyl nitrate, secondary amyl nitrate, isoamyl nitrate, primary hexyl nitrate, Various nitrates such as secondary hexyl nitrate, n-heptyl nitrate, n-octyl nitrate, 2-ethylhexyl nitrate, cyclohexyl nitrate, and ethylene glycol dinitrate are included. An alkyl nitrate of ˜8 is preferred.

  The content of the cetane improver is preferably 500 ppm by mass or more based on the total amount of the composition, more preferably 600 ppm by mass or more, further preferably 700 ppm by mass or more, and 800 ppm by mass or more. It is particularly preferable that it is 900 mass ppm or more. When the content of the cetane number improver is less than 500 ppm by mass, a sufficient cetane number improving effect cannot be obtained, and PM, aldehydes, and further NOx in diesel engine exhaust gas tend not to be sufficiently reduced. Further, the upper limit of the content of the cetane number improver is not particularly limited, but is preferably 1400 mass ppm or less, more preferably 1250 mass ppm or less, based on the total amount of the light oil composition, and 1100 mass ppm or less. It is more preferable that it is 1000 mass ppm or less.

  As the cetane number improver, one synthesized according to a conventional method may be used, or a commercially available product may be used. In addition, what is marketed as a cetane number improver is usually obtained in a state where an active ingredient contributing to cetane number improvement (that is, cetane number improver itself) is diluted with an appropriate solvent. When preparing the light oil composition of this invention using such a commercial item, it is preferable that content of the said active ingredient in a light oil composition becomes in the above-mentioned range.

  In the light oil composition of the present invention, additives other than the cetane number improver can be blended as necessary, and in particular, a lubricity improver and / or a detergent is preferably blended.

  As the lubricity improver, for example, one or more of carboxylic acid-based, ester-based, alcohol-based and phenol-based lubricity improvers can be arbitrarily used. Among these, carboxylic acid-based and ester-based lubricity improvers are preferable. Examples of the carboxylic acid-based lubricity improver include linoleic acid, oleic acid, salicylic acid, palmitic acid, myristic acid, hexadecenoic acid, and a mixture of two or more of the above carboxylic acids. Examples of ester-based lubricity improvers include carboxylic acid esters of glycerin. The carboxylic acid constituting the carboxylic acid ester may be one kind or two or more kinds, and specific examples thereof include linoleic acid, oleic acid, salicylic acid, palmitic acid, myristic acid, hexadecenoic acid and the like. There is.

  The blending amount of the lubricity improver needs to be 50 mass ppm or more and 300 mass ppm or less, preferably 75 mass ppm or more and 200 mass ppm or less, more preferably 100 mass ppm or more and 150 mass ppm or less. When the blending amount of the lubricity improver is within the above range, the effectiveness of the blended lubricity improving agent can be effectively extracted. For example, in a diesel engine equipped with a distributed injection pump, An increase in driving torque can be suppressed and pump wear can be reduced.

  Examples of the detergent include imide compounds; alkenyl succinimides such as polybutenyl succinimides synthesized from polybutenyl succinic anhydrides and ethylene polyamines; polyhydric alcohols such as pentaerythritol and polybutyls. Succinic acid esters such as polybutenyl succinic acid ester synthesized from tenyl succinic anhydride; copolymer polymers such as dialkylaminoethyl methacrylate, polyethylene glycol methacrylate, vinyl pyrrolidone and alkyl methacrylate copolymers, carboxylic acids and amines Ashless detergents such as reaction products of alkenyl succinic acid imide and reaction products of carboxylic acid and amine are preferred. These detergents can be used alone or in combination of two or more.

  Examples of using an alkenyl succinimide include a case where an alkenyl succinimide having a molecular weight of about 1000 to 3000 is used alone, an alkenyl succinimide having a molecular weight of about 700 to 2000, and an alkenyl succinimide having a molecular weight of about 10,000 to 20000. May be used in combination. The carboxylic acid constituting the reaction product of the carboxylic acid and the amine may be one type or two or more types. Specific examples thereof include fatty acids having 12 to 24 carbon atoms and carbon atoms having 7 to 24 carbon atoms. An aromatic carboxylic acid etc. are mentioned. Examples of the fatty acid having 12 to 24 carbon atoms include linoleic acid, oleic acid, palmitic acid, myristic acid and the like, but are not limited thereto. In addition, examples of the aromatic carboxylic acid having 7 to 24 carbon atoms include benzoic acid and salicylic acid, but are not limited thereto. Moreover, the amine which comprises the reaction product of carboxylic acid and an amine may be 1 type, or may be 2 or more types. The amine used here is typically oleylamine, but is not limited thereto, and various amines can be used.

  The blending amount of the cleaning agent is not particularly limited, but in order to bring out the effect of blending the cleaning agent, specifically, the effect of suppressing clogging of the fuel injection nozzle, the blending amount of the cleaning agent is 30 mass ppm based on the total amount of the composition. It is preferable to set it as the above, It is more preferable to set it as 60 mass ppm or more, It is further more preferable to set it as 80 mass ppm or more. Even if an amount less than 30 ppm by mass is added, the effect may not appear. On the other hand, if the amount is too large, an effect commensurate with that cannot be expected, and conversely, NOx, PM, aldehydes, etc. in the diesel engine exhaust gas may increase, so the amount of detergent contained is 300 mass. It is preferably not more than ppm, and more preferably not more than 180 mass ppm.

  As in the case of the previous cetane improver, those commercially available as a lubricity improver or a detergent are those in which the active ingredients that contribute to improving lubricity or cleaning are diluted with an appropriate solvent, respectively. It is usually obtained at When such a commercial product is blended in the light oil composition of the present invention, the content of the active ingredient in the light oil composition is preferably within the above range.

  Further, for the purpose of further enhancing the performance of the light oil composition in the present invention, other known fuel oil additives (hereinafter referred to as “other additives” for convenience) to be described later are added alone or in combination of several kinds. You can also. Other additives include, for example, low-temperature fluidity improvers such as ethylene-vinyl acetate copolymer and alkenyl succinic acid amide; antioxidants such as phenols and amines; metal deactivators such as salicylidene derivatives; Anti-icing agents such as polyglycol ethers; corrosion inhibitors such as aliphatic amines and alkenyl succinic acid esters; antistatic agents such as anionic, cationic and amphoteric surfactants; colorants such as azo dyes; Antifoaming agents and the like.

  The addition amount of other additives can be arbitrarily determined, but the addition amount of each additive is preferably 0.5% by mass or less, more preferably 0.2% by mass or less, based on the total amount of the light oil composition. is there.

  EXAMPLES Hereinafter, although this invention is demonstrated further in detail 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.

  2. 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 (II) nitrate 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.

[Manufacture of light oil base]
Example 1
In Example 1, vegetable oil (palm oil) having the properties shown in Table 2 and an aliphatic hydrocarbon compound having a mass ratio of 1.0 with respect to the vegetable oil are mixed, and a sulfur compound ( DMDS (dimethyl disulfide) was added to the palm oil in an amount of 5 ppm by mass (in terms of sulfur atoms) to prepare an oil to be treated. In addition, the aliphatic hydrocarbon compound used in the present Example is a recycle oil obtained by subjecting the oil to be treated to a hydrotreatment under the conditions described later and recycling the obtained hydrocarbon fraction.

  The oil to be treated was hydrotreated under the reaction condition 1 shown in Table 3, and a fraction having a boiling point range of 200 to 350 ° C. was fractionated in a rectifying column to obtain a target light oil base material. Table 4 shows various properties of the obtained light oil base. In addition, the “recycling ratio” in Table 3 means the mass ratio of the recycled oil (aliphatic hydrocarbon compound) to the vegetable oil in the oil to be treated. The amount of catalyst charged into the reactor was 50 cc.

(Comparative Example 1)
A light oil base was produced in the same manner as in Example 1 except that the hydrogenation treatment was performed under the reaction condition 2 shown in Table 3. Table 4 shows various properties of the obtained light oil base.

(Comparative Example 2)
A light oil base was produced in the same manner as in Example 1 except that the hydrogenation treatment was performed under the reaction condition 3 shown in Table 3. Table 4 shows various properties of the obtained light oil base.

(Comparative Example 3)
The vegetable oil and fat shown in Table 3 was esterified to obtain an alkyl esterified product of the vegetable oil and fat. The alkyl esterified product of vegetable oil is a methyl ester compound obtained by the reaction of vegetable oil and methanol. Here, stirring is performed at 70 ° C. for about 1 hour in the presence of an alkali catalyst (sodium methylate). A transesterification reaction was performed by directly reacting with an alkyl alcohol to obtain an ester compound. Table 5 shows the properties of the obtained vegetable oil methyl ester.

  Table 5 also shows a hydrorefining lamp / light oil fraction obtained by hydrorefining a straight-run light / light oil fraction obtained from a crude oil atmospheric distillation apparatus used in the production of the light oil composition described below. The properties of the hydrorefined oils 1 and 2 are also shown.

[Preparation of light oil composition]
(Examples 2 and 3, Comparative Examples 4 to 7)
In Examples 2 and 3 and Comparative Examples 4 to 7, the hydrotreated oils 1 to 3 shown in Table 4 and the vegetable oil methyl ester and the hydrorefined oils 1 and 2 shown in Table 5 are shown in Tables 6 and 7, respectively. A light oil composition was prepared by adding a low temperature fluidity improver (ethylene-vinyl acetate copolymer) at a concentration shown in Tables 6 and 7 to the light oil base material mixture. Density at 15 ° C., kinematic viscosity at 30 ° C., flash point, sulfur content, oxygen content, cloud point, clogging point, (cloud point-clogging point), distillation properties, cetane number, 10% remaining Tables 6 and 7 show the residual carbon content, fatty acid methyl ester content, methanol content, glyceride content, and acid value of the oil.

The properties of the fuel oil were measured by the following method.
As described above, the total paraffin amount and normal paraffin amount were obtained by using a gas chromatograph / time-of-flight mass spectrometer (GC-TOFMS). The measurement apparatus and measurement conditions in the present invention are shown below.
(GC department)
Equipment: HEWLETT PACKARD, HP6890 Series GC System & Injector
Column: A client HP-5 (30 m × 0.32 mmφ, 0.25 μm-film)
Carrier gas: He, 1.4 mL / min (constant flow)
Inlet temperature: 320 ° C
Injection mode: split (split ratio = 1: 100)
Oven temperature: held at 50 ° C. for 5 minutes, heated at 5 ° C./minute, and held at 320 ° C. for 6 minutes.
Injection volume: 1 μL
(TOFMS Department)
Device: JEOL Ltd., JMS-T100GC
Counter electrode voltage: 10.0 kV
Ionization method: FI + (field ionization)
GC interface temperature: 250 ° C
Measurement mass range: 35-500.
The density refers to a density measured according to JIS K 2249 “Determination method of density of crude oil and petroleum products and density / mass / capacity conversion table”.
The kinematic viscosity refers to a kinematic viscosity measured according to JIS K 2283 “Crude oil and petroleum products—Kinematic viscosity test method and viscosity index calculation method”.
The flash point indicates a value measured according to JIS K 2265 “Crude oil and petroleum product flash point test method”.
The sulfur content refers to the mass content of the sulfur content based on the total amount of the gas oil composition measured by JIS K2541 “Sulfur content test method”.
The oxygen content was measured by elemental analysis.
The cloud point means a cloud point measured by JIS K 2269 “Crude point of petroleum and petroleum products and petroleum product cloud point test method”.
The clogging point refers to a clogging point measured by JIS K 2288 “Light oil—clogging point test method”.
All the distillation properties are values measured by JIS K 2254 "Petroleum products-Distillation test method".
The aromatic content is the volume percentage of the aromatic content measured according to the Petroleum Institute Method JPI-5S-49-97 “Hydrocarbon Type Test Method—High Performance Liquid Chromatograph Method” published by the Japan Petroleum Institute. (Capacity%).
The acid value means an acid value measured according to JIS K 2501 “Petroleum products and lubricants—neutralization number test method”.
The cetane number means a cetane number measured according to “7. Cetane number test method” of JIS K 2280 “Petroleum products—fuel oil—octane number and cetane number test method and cetane index calculation method”.
The residual carbon content of 10% residual oil means the residual carbon content of 10% residual oil measured by JIS K 2270 “Crude oil and petroleum products—residual carbon content test method”.
The fatty acid methyl ester content means the fatty acid methyl ester content measured according to EN14103.
A triglyceride content shows the value measured based on EN14105.

[Evaluation of life cycle CO ₂ ]
The life cycle CO ₂ is referred to as CO ₂ generated by combustion of the light oil composition in a vehicle equipped with a diesel engine (hereinafter referred to as “Tank to Wheel CO ₂ ”).
) And CO ₂ generated from mining to fueling the vehicle tank (hereinafter referred to as “Well to Tank CO ₂ ”).
Tank to Wheel CO ₂ was calculated as the emission amount per unit calorific value of each light oil composition based on the CO ₂ emission amount, the running fuel consumption, and the fuel density when the vehicle test was performed.
Well to Tank CO ₂ was calculated as the sum of CO ₂ emissions in a series of flows from mining, transportation, processing, delivery and refueling of raw materials and crude oil sources. In calculating Well to Tank CO ₂ , calculation was performed in consideration of the carbon dioxide emission shown in the following (1B) to (5B). As data necessary for such calculation, refinery operation performance data possessed by the present inventors was used.
(1B) Carbon dioxide emissions associated with the use of fuel in various processing equipment, boilers and other facilities.
(2B) In the treatment using hydrogen, the amount of carbon dioxide emission accompanying the reforming reaction in the hydrogen production apparatus.
(3B) Carbon dioxide emission associated with catalyst regeneration when passing through an apparatus with continuous catalyst regeneration, such as a catalytic cracker.
(4B) Carbon dioxide emissions when a light oil composition is manufactured or unloaded in Yokohama, delivered from Yokohama to Sendai, and refueled in Sendai.
(5B) The amount of carbon dioxide emission when animal and vegetable oils and fats and components derived from animal and vegetable oils and fats are produced in Malaysia and the surrounding area and manufactured in Yokohama.
In addition, when using animal and vegetable oils and fats and components derived from animal and vegetable oils and fats, the so-called Kyoto Protocol applies the rule that carbon dioxide resulting from these fuels is not counted as emissions. In this calculation, this was applied to “Tank to Wheel CO ₂ ” generated during combustion.
The obtained results are shown in Tables 6 and 7.

(Oxidation stability test)
The fuel was accelerated and deteriorated at 115 ° C. under oxygen bubbling for 16 hours, and the oxidation before and after the test was measured. In addition, an acid value here means the acid value measured by JISK2501 "Petroleum products and lubricating oil-neutralization number test method". The obtained results are shown in Tables 6 and 7.

  As is apparent from Tables 6 and 7, in Examples 2 and 3, 90% distillation temperature is 360 ° C. or lower, flash point 45 ° C. or higher, cetane number is 50 or higher, clogging point −5 ° C. or lower (cloudiness) (Point-clogging point) value is + 5 ° C. or higher, sulfur content is 10 mass ppm or less, oxygen content is 1 mass% or less, triglyceride content is 0.01 mass% or less, fatty acid alkyl ester content is 3.5 mass% or less, acid value A light oil composition having an acid value increase of 0.12 mgKOH / g or less after an oxidation stability test of 0.13 mgKOH / g or less could be obtained easily and reliably. On the other hand, in the comparative examples 4-7 which prepared the light oil composition, without using the said specific light oil base material (Example 1), the light oil composition made into the objective of this invention was not obtained.

Claims (4)

In the presence of hydrogen, an oxygenated hydrocarbon compound derived from animal and vegetable oils, an aliphatic hydrocarbon compound, and a sulfur-containing hydrocarbon compound are blended , and the sulfur content of the oxygenated hydrocarbon compound is converted to a sulfur atom. 1 to 50 ppm by weight of the oil to be treated is made of a porous inorganic oxide comprising two or more elements selected from aluminum, silicon, zirconium, boron, titanium and magnesium, and the porous inorganic oxide. Using a catalyst containing one or more metals selected from Group 6A and Group 8 elements of the supported periodic table, hydrogen pressure 1-6 MPa, liquid space velocity 0.1-0.7 h ⁻¹ , by hydrotreating at a reaction temperature from 250 to 365 ° C., Bruno Rumaru and the content of paraffin 90% by mass or more, the defined carbon number n (10 ≦ n ≦ 20 in the hydrocarbon fraction; n is even . Which are shown) in the total paraffin content of _{A n} (unit: mass%), _B the total paraffin content in the carbon number of _n-1 n-1 (unit: mass%), the ratio of _{B n-1} with respect to _{A n} And (B _n-1 / A _n ), the step of obtaining a light oil base material in which the average value of (B _n-1 / A _n ) in 10 ≦ n ≦ 20 is 0.30 or more is provided. A method for producing a light oil base material. The method for producing a light oil base material according to claim 1, wherein the oxygen-containing hydrocarbon compound derived from the animal and vegetable oil is at least one compound selected from fatty acids and fatty acid esters. The method for producing a light oil base material according to claim 1 or 2, wherein the fatty acid esters are triglycerides of fatty acids. A step of obtaining a first light oil base by the production method according to any one of claims 1 to 3 ,
90% distillation by blending the second light oil base containing 10% by volume or more of the first light oil base and a low temperature fluidity improver of 10 to 1000 mass ppm based on the total amount of the light oil composition. The temperature is 360 ° C. or less, the sulfur content is 10 mass ppm or less, the oxygen content is 1 mass% or less, the fatty acid alkyl ester content is 3.5 mass% or less, the acid value is 0.13 mg KOH / g or less, the methanol content is 0.01 mass% or less, A step of obtaining a light oil composition having a glyceride content of 0.01% by mass or less and a clogging point of −5 ° C. or less ;
A process for producing a light oil composition, comprising :