Method for estimating PM generation amount, method for producing fuel oil composition, and fuel oil composition

Abstract

Provided is a method for estimating the amount of PM produced from the characteristics of a fuel oil composition. A method for estimating the amount of PM produced, comprising the step of calculating an estimated value of the amount of PM produced based on the following formula (1). M=0.044×V AB +0.065×V NB +0.091×V PA +0.017×V N1 +0.040×V PN +0.027×(T10-220)+0.018×(T90-330)+C···(1) In the above formula (1), M represents an estimated value of the amount of PM produced [mg], and C is an arbitrary constant set in advance. Further, V AB , V NB , V PA , V N1 , and V PN each represent the content [volume%] based on the total amount (100 volume%) of the fuel oil composition of an alkylbenzene content, a naphthenobenzene content, a 2 or more-ring aromatic content, a 1-ring naphthene content, and a 2 or more-ring naphthene content, respectively. Further, T10 represents the 10 volume% distillation temperature [°C] of the fuel oil composition, and T90 represents the 90 volume% distillation temperature [°C] of the fuel oil composition.

Description

[Technical Field]

[0001] This disclosure relates to a method for estimating PM generation, a method for producing a fuel oil composition, and a fuel oil composition. [Background technology]

[0002] Among fuel oil compositions, diesel fuel, which is mainly used in large vehicles, is less susceptible to being replaced by other energy sources such as electricity or hydrogen, unlike gasoline and heavy oil. Therefore, even as demand for other fuels is expected to decrease, the demand for diesel fuel is projected to remain relatively high, and there is a need to increase diesel fuel production. Specific methods include mixing in LCO (Light Cycle Oil), which is used for A heavy fuel oil, which has seen a greater decline in demand than diesel fuel, mixing in kerosene fractions, and adjusting the distillation cutoff temperature.

[0003] Generally, decomposition-type substrates contain a large amount of aromatic compounds, but it is known that diesel fuel with a high aromatic content has poor flammability and tends to increase the amount of PM (particulate matter) generated, which is a cause of air pollution. For example, Patent Document 1 describes a method for suppressing PM weight and particle count by controlling the total aromatic content, bi-ring aromatic content, tri-ring or more aromatic content, density at 15°C, kinematic viscosity at 30°C, pour point, and 90% distillation temperature of diesel fuel. However, Patent Document 1 limits the total aromatic content of diesel fuel to a low level of 11.0 to 16.0% by volume, and is not a suitable method when it is desired to increase the processing ratio of decomposition-type substrates that contain a large amount of aromatic content. [Prior art documents] [Patent Documents]

[0004] [Patent Document 1] Japanese Patent Publication No. 2010-132722 [Overview of the project] [Problems that the invention aims to solve]

[0005] Although methods for suppressing PM generation by adjusting the composition and distillation properties of diesel fuel have been proposed, as described in Patent Document 1, there are no examples of quantitatively examining the relationship between diesel fuel characteristics and PM generation. Essentially, it is necessary to verify the quality of each diesel fuel produced through experiments, but such experiments are time-consuming, laborious, and burdensome. Under these circumstances, in order to further promote the use of decomposition-based substrates, there is a need for a method to estimate the amount of PM generation in advance from the characteristics of diesel fuel and to produce diesel fuel in which PM generation is suppressed even when the processing ratio of decomposition-based substrates is increased.

[0006] The purpose of this disclosure is to provide a method for estimating PM generation amount that enables estimation of PM generation amount from the characteristics of a fuel oil composition, a method for producing a fuel oil composition using the estimation method, and a fuel oil composition. [Means for solving the problem]

[0007] The disclosing parties have diligently considered how to resolve the above-mentioned issues. As a result, we have come to realize that the above issues can be resolved by disclosing the following. In other words, the following [1] to [4] are provided by this disclosure. [1] A method for estimating the amount of PM generated during the operation of an internal combustion engine, based on the characteristics of the fuel oil composition used during the operation of the internal combustion engine, A method for estimating PM generation, which includes the step of calculating an estimated value of PM generation based on the following formula (1). M = 0.044 × V AB +0.065 × V NB +0.091 × V PA +0.017 × V N1 +0.040 × V PN +0.027×(T10-220)+0.018×(T90-330)+C...(1) However, in equation (1) above, M represents the estimated amount of PM produced [mg], and C is a predetermined arbitrary constant. Also, V AB, V NB , V PA , V N1 , and V PN each represent the content [vol%] of the following components based on the total amount (100 vol%) of the fuel oil composition. V AB : alkylbenzene content V NB : naphthenobenzene content V PA : aromatics with two or more rings V N1 : monocyclic naphthene content V PN : naphthenes with two or more rings Further, T10 represents the 10% by volume distillation temperature [°C] of the fuel oil composition, and T90 represents the 90% by volume distillation temperature [°C] of the fuel oil composition. [2] A method for producing a fuel oil composition, comprising: A method for producing a fuel oil composition, comprising a step of controlling the composition of the fuel oil composition such that an estimated value M of the amount of PM produced when an internal combustion engine is operated using the fuel oil composition represented by the following formula (1) is equal to or less than a preset threshold value. M=0.044×V AB +0.065×V NB +0.091×V PA +0.017×V N1 +0.040×V PN +0.027×(T10-220)+0.018×(T90-330)+C···(1) However, in the above formula (1), M represents the estimated value [mg] of the amount of PM produced, and C is an arbitrary preset constant. Further, V AB , V NB , V PA , V N1 , and V PN each represent the content [vol%] of the following components based on the total amount (100 vol%) of the fuel oil composition. V AB : alkylbenzene content V NB : naphthenobenzene content V PA : aromatics with two or more rings V N1 :1 ring naphthene V PN : Naphthenes of 2 or more rings Furthermore, T10 represents the 10% volume distillation temperature [°C] of the fuel oil composition, and T90 represents the 90% volume distillation temperature [°C] of the fuel oil composition. [3] A fuel oil composition manufactured by the manufacturing method described in [2]. [4] A fuel oil composition, A fuel oil composition in which the estimated amount M of PM generated when an internal combustion engine is operated using the fuel oil composition, as represented by the following formula (1), is 2.7 mg or less. M = 0.044 × V AB +0.065 × V NB +0.091 × V PA +0.017 × V N1 +0.040 × V PN +0.027×(T10-220)+0.018×(T90-330)+C...(1) However, in equation (1) above, M represents the estimated amount of PM produced [mg], and C is a predetermined arbitrary constant. Also, V AB , V NB , V PA , V N1 , and V PN These values ​​represent the content [volume %] of the following components based on the total amount (100 volume %) of the fuel oil composition. V AB : Alkylbenzene V NB : Naphthenobenzene V PA : 2 or more rings of aroma V N1 :1 ring naphthene V PN : Naphthenes of 2 or more rings Furthermore, T10 represents the 10% volume distillation temperature [°C] of the fuel oil composition, and T90 represents the 90% volume distillation temperature [°C] of the fuel oil composition. [Effects of the Invention]

[0008] According to this disclosure, it is possible to provide a method for estimating PM generation amount that enables estimation of PM generation amount from the characteristics of a fuel oil composition, a method for producing a fuel oil composition using the estimation method, and a fuel oil composition. [Modes for carrying out the invention]

[0009] The upper and lower limits of the numerical ranges described herein can be combined in any way. For example, if the numerical ranges "A to B" and "C to D" are described, the numerical ranges "A to D" and "C to B" are also included within the scope of this disclosure. Furthermore, unless otherwise specified, the numerical range "lower limit to upper limit" described herein means that the value is greater than or equal to the lower limit and less than or equal to the upper limit.

[0010] The following details the PM generation estimation method described in this disclosure.

[0011] [Method for estimating PM generation amount] The PM generation amount estimation method in this disclosure is a method for estimating the PM generation amount during the operation of an internal combustion engine based on the characteristics of the fuel oil composition used during the operation of the internal combustion engine, and includes the step of calculating an estimated value of the PM generation amount based on the following formula (1). M = 0.044 × V AB +0.065 × V NB +0.091 × V PA +0.017 × V N1 +0.040 × V PN +0.027×(T10-220)+0.018×(T90-330)+C...(1) However, in equation (1) above, M represents the estimated amount of PM produced [mg], and C is a predetermined arbitrary constant. Also, V AB , V NB , V PA , V N1 , and V PN These values ​​represent the content [volume %] of the following components based on the total amount (100 volume %) of the fuel oil composition. VAB : Alkylbenzene V NB : Naphthenobenzene V PA : 2 or more rings of aroma V N1 :1 ring naphthene V PN : Naphthenes of 2 or more rings Furthermore, T10 represents the 10% volume distillation temperature [°C] of the fuel oil composition, and T90 represents the 90% volume distillation temperature [°C] of the fuel oil composition. The constant term C in equation (1) above can be derived, for example, from the relationship between the measured PM generation amount of the fuel oil composition measured by the method described in the examples below and the estimated PM generation amount M of the fuel oil composition obtained by equation (1) above. The possible values ​​of C are, for example, 0.00 to 1.00, 0.10 to 0.80, 0.20 to 0.40, or 0.29. Furthermore, as a method for measuring the actual amount of PM generated by the aforementioned fuel oil composition, for example, as described in the examples below, an exhaust gas test can be performed using a test vehicle with the following specifications at an intake air temperature of 25°C and humidity of 50%, in the JE05 mode specified in the "Notification Specifying the Details of Safety Standards for Road Vehicles [2008.03.25] Appendix 41 (Measurement Method for Exhaust Gas from Heavy Vehicles)" issued by the Ministry of Land, Infrastructure, Transport and Tourism. The PM can then be measured by connecting a microtunnel to the exhaust pipe at the inlet of the aftertreatment device (including oxidation catalyst and DPF) of the vehicle used and collecting the generated PM with a collection filter. (Engine specifications) Engine type: Inline 4-cylinder diesel • Engine displacement: 3.0L Engine maximum output: 110kW / 2800rpm Engine maximum torque: 375Nm / 1400~2800rpm Engine bore x stroke: 95.4mm x 104.9mm • Compression ratio: 15.8 • Regulatory compliance: Complies with post-new long-term exhaust gas regulations.

[0012] The Disclosing Parties conducted intensive studies to solve the above-mentioned problems. As a result, they found that the amount of PM generated by fuel oil compositions differs significantly not only from the influence of composition other than aromatic components (especially naphthenes) and the number of rings and side chains of aromatic components (whether they are alkylbenzenes or naphthenobenzenes), but also from differences in lightening methods such as mixing in light fractions and cutting off heavy components.

[0013] Therefore, the inventors conducted further intensive studies and found that, as a characteristic of the fuel oil composition, particularly V AB (Alkylbenzene content), V NB (Naphthenobenzene content), V PA (2 or more rings of aroma), V N1 (1-ring naphthene component), and V PN We discovered that (naphthenes with two or more rings) affect PM generation, and after further investigations, we completed the present invention.

[0014] <Characteristics of fuel oil composition> The characteristics of the fuel oil composition used in the PM generation estimation method of this disclosure will be described in detail below.

[0015] (V AB (Alkylbenzene content) V in the method for estimating PM generation amount in this disclosure AB This represents the alkylbenzene content [volume %] based on the total volume (100 volume %) of the fuel oil composition in question. In this disclosure, the alkylbenzene component contained in the fuel oil composition is a monocyclic aromatic molecule in which one or more hydrogen atoms are replaced by one or more alkyl groups, and examples of such alkyl groups include linear or branched alkyl groups having 2 to 6 carbon atoms. Examples of the alkylbenzene component include, for example, pentamethylbenzene, hexamethylbenzene, 1-ethyl-3-methylbenzene, trimethylbenzene, 1-ethyl-3,5-dimethylbenzene, 1-methyl-4-propylbenzene, and 2-methyl-1,3-dimethylbenzene. Furthermore, in this disclosure, V ABSpecifically, this can be measured by the method described in the examples below. In this disclosure, V AB The value of is not particularly restricted, but for example, it is between 2.0 and 25.0 volume%.

[0016] (V NB (Naphthenobenzene content) V in the method for estimating PM generation amount in this disclosure NB This represents the naphthenobenzene content [volume %] based on the total volume (100 volume %) of the fuel oil composition in question. In this disclosure, the naphthenobenzene component contained in the fuel oil composition is a compound in which one ring aromatic and one or more naphthene rings coexist within a single molecule, and the number of carbon atoms in the naphthene ring is, for example, 5 to 6. Examples of the naphthenobenzene component include indan, tetralin, and the like. In this disclosure, if a monocyclic aromatic compound has both an alkyl group and a naphthene ring as substituents, the monocyclic aromatic compound is treated as "naphthenobenzene". Furthermore, in this disclosure, V NB Specifically, this can be measured by the method described in the examples below. In this disclosure, V NB The value is not particularly restricted, but for example, it is between 1.0 and 25.0 volume%.

[0017] (V PA (Aromatic components of 2 or more rings) V in the method for estimating PM generation amount in this disclosure PA This represents the content [volume %] of two or more aromatic compounds based on the total amount (100 volume %) of the fuel oil composition in question. In this disclosure, the two or more ring aromatic components contained in the fuel oil composition have two or more benzene rings and may be substituted or unsubstituted, for example, having 2 to 4 benzene rings. Examples of the two or more ring-containing aromatic compounds include naphthalene, 1-methylnaphthalene, acenaphthene, biphenyl, fluorene, and phenanthrene. Furthermore, in this disclosure, V PA Specifically, this can be measured by the method described in the examples below. In this disclosure, V PA The value of is not particularly restricted, but for example, it is between 0.1 and 15.0 volume%.

[0018] (V N1 (1-ring naphthene component) V in the method for estimating PM generation amount in this disclosure N1 This represents the monocyclic naphthene content [volume %] based on the total amount (100 volume %) of the fuel oil composition in question. In this disclosure, the mono-ring naphthene component contained in the fuel oil composition has one naphthene ring and no benzene ring, and may be substituted or unsubstituted, with the number of carbon atoms in the naphthene ring being, for example, 5 to 6. Examples of the monocyclic naphthene component include cyclopentane and cyclohexane. Furthermore, in this disclosure, V N1 Specifically, this can be measured by the method described in the examples below. In this disclosure, V N1 The value of is not particularly restricted, but for example, it is between 2.0 and 25.0 volume%.

[0019] (V PN (2 or more naphthenes) V in the method for estimating PM generation amount in this disclosure PN This represents the content [volume %] of two or more naphthenes based on the total amount (100 volume %) of the fuel oil composition in question. In this disclosure, the two or more naphthene components contained in the fuel oil composition are those having two or more naphthene rings and no benzene rings, and may be substituted or unsubstituted, with the total number of carbon atoms in the two or more naphthene rings being, for example, 8 to 10. Examples of such two-ring or more naphthene components include, for instance, decalin. Furthermore, in this disclosure, V PN Specifically, this can be measured by the method described in the examples below. In the present disclosure, V PN is not particularly limited, and is, for example, 2.0 to 25.0% by volume.

[0020] (T10 (10 volume percent distillation temperature), T90 (90 volume percent distillation temperature)) In the method for estimating the PM production amount of the present disclosure, T10 and T90 are respectively the 10 volume percent distillation temperature [°C] and the 90 volume percent distillation temperature [°C] of the target fuel oil composition. In the present disclosure, T10 and T90 are values measured in accordance with JIS K2254:2018 (Petroleum products - Determination of distillation characteristics - Atmospheric pressure method). In the present disclosure, the value of T10 is not particularly limited, and is, for example, 170 to 260°C. Further, the value of T90 is also not particularly limited, and is, for example, 270 to 360°C.

[0021] (Use of Fuel Oil Composition) The use of the fuel oil composition to which the method for estimating PM production amount of the present disclosure is applicable is not particularly limited, but the fuel oil composition is preferably used as a gas oil composition. Further, the fuel oil composition is preferably used when operating an internal combustion engine, more preferably when operating a diesel engine.

[0022] [Method for Producing Fuel Oil Composition] The method for producing a fuel oil composition of the present disclosure is a method for producing a fuel oil composition, comprising a step of controlling the composition of the fuel oil composition such that an estimated value M of the PM production amount when an internal combustion engine is operated using the fuel oil composition represented by the following formula (1) is equal to or less than a preset threshold value. M=0.044×V AB +0.065×V NB +0.091×V PA +0.017×V N1 +0.040×V PN +0.027×(T10-220)+0.018×(T90-330)+C···(1) However, in the above formula (1), M represents an estimated value [mg] of the PM production amount, and C is any preset constant. Further, V AB , V NB , V PA , V N1 , and V PN each represent the content [vol%] of the following components based on the total amount (100 vol%) of the fuel oil composition. V AB : alkylbenzene content V NB : naphthenobenzene content V PA : aromatics with two or more rings V N1 : monocyclic naphthene content V PN : naphthenes with two or more rings Further, T10 represents the 10% by volume distillation temperature [°C] of the fuel oil composition, and T90 represents the 90% by volume distillation temperature [°C] of the fuel oil composition. Note that details of the constant term C in the above formula (1) are as described above.

[0023] <Threshold for estimated PM generation amount M> In the method for producing a fuel oil composition according to the present disclosure, as described above, by controlling the characteristics of the fuel oil composition (V AB , V NB , V PA , V N1 , V PN , T10, and T90), the PM generation amount can be controlled. Therefore, even if the treatment ratio of cracked base materials having a high aromatic content is generally increased, the fuel oil composition can be produced while suppressing the PM generation amount. Since the aforementioned characteristics of the fuel oil composition can be adjusted by controlling the composition of the fuel oil composition, the PM generation amount can be controlled by controlling the composition of the fuel oil composition. Further, the method for producing a fuel oil composition according to the present disclosure includes a step of setting a threshold for the estimated PM generation amount M, and adjusting the composition of the fuel oil composition such that the estimated PM generation amount M is equal to or less than the threshold.

[0024] The threshold value M for the estimated amount of PM generated is set based on the performance required of the fuel oil composition and the standards stipulated by law, and there are no particular restrictions on how it is set, but the following methods are examples.

[0025] PM (particulate matter) is a fine particulate matter, and when its generation increases, it can cause clogging of the DOC (Diesel Oxidation Catalyst) and DPF (Diesel Particulate Filter) installed in diesel vehicles. DPF regeneration is necessary to clear the clogging. DPF regeneration is a method that raises the temperature of the exhaust gas to burn the PM clogging the DPF and remove the PM accumulated in the filter. There are two types of regeneration: forced regeneration, which is performed at the driver's discretion, and automatic regeneration, which is performed automatically when the vehicle detects the clogging status of the DPF. By evaluating the relationship between the estimated PM generation amount M and the clogging of the DOC and DPF (differential pressure in the DOC and DPF), a threshold can be set for the estimated PM generation amount M at which the clogging of the DOC and DPF falls below the required performance level. Specifically, for example, by changing the estimated value M of the PM generation amount of the fuel oil composition and performing a driving test using the method described in the examples below, the estimated value M of the PM generation amount of the fuel oil composition when a problem occurs in which the DOC differential pressure does not return to its original state even after forced regeneration, and when the DPF regeneration interval (the number of JE05 mode tests that can be performed before the DPF is forced to regenerate) is shortened, can be found, and the value of M that represents the critical point at which these problems do not occur can be set as a threshold.

[0026] As mentioned above, the threshold value M for the estimated PM generation is set according to the performance required of the fuel oil composition and the standards stipulated by law, and is not particularly limited, but for example it can be set to 2.7 mg. In other words, the method for producing the fuel oil composition of this disclosure may include a step of controlling the composition of the fuel oil composition so that the estimated value M of PM generation is 2.7 mg or less.

[0027] <Process for controlling the composition of fuel oil composition> In the method for producing the fuel oil composition of the present disclosure, the steps for controlling the composition of the fuel oil composition are not particularly limited, but examples include the following methods. In addition, in the above equation (1), V AB , V NB , V PA , V N1 , V PN Since the coefficients for the T10 and T90 terms are all positive, the estimated PM generation amount M can be reduced by decreasing the value of each characteristic.

[0028] (V AB (Control method) V of fuel oil composition AB This can be controlled, for example, by adjusting the reaction temperature of the desulfurization equipment. Specifically, for example, when desulfurizing a fuel oil composition, the V of the fuel oil composition can be controlled by lowering the reaction temperature of the desulfurization equipment. AB The value can be lowered.

[0029] (V NB (Control method) V of fuel oil composition NB This can be controlled, for example, by adjusting the reaction temperature of the desulfurization equipment. Specifically, for example, when desulfurizing a fuel oil composition, the V of the fuel oil composition can be controlled by lowering the reaction temperature of the desulfurization equipment. NB The value can be lowered.

[0030] (V PA (Control method) V of fuel oil composition PA This can be controlled, for example, by adjusting the reaction temperature of the desulfurization equipment. Specifically, for example, when desulfurizing a fuel oil composition, the V of the fuel oil composition can be controlled by lowering the reaction temperature of the desulfurization equipment. PA The value can be lowered.

[0031] (V N1 (Control method) V of fuel oil composition N1This can be controlled, for example, by the mixing ratio of a base material (pyrolytic oil) obtained by pyrolysis, such as light coker gas oil (LCGO). Specifically, for example, by lowering the mixing ratio of pyrolytic oil in the fuel oil composition, the V of the fuel oil composition can be controlled. N1 The value can be lowered.

[0032] (V PN (Control method) V of fuel oil composition PN This can be controlled, for example, by the mixing ratio of the pyrolysis-based oils mentioned above. Specifically, for example, by lowering the mixing ratio of pyrolysis-based oils in the fuel oil composition, the V of the fuel oil composition can be controlled. PN The value can be lowered.

[0033] (Control method for T10) The T10 of a fuel oil composition can be controlled, for example, by mixing in kerosene or a light solvent (such as an isoparaffinic solvent). Specifically, for example, the value of T10 of a fuel oil composition can be lowered by increasing the mixing ratio of kerosene or a light solvent in the fuel oil composition.

[0034] (T90 control method) The T90 of a fuel oil composition can be controlled, for example, by removing the heavy portion through distillation. Specifically, the T90 value of the fuel oil composition can be lowered by removing a large amount of the heavy portion through distillation.

[0035] Furthermore, the base materials that can be used in the manufacturing method of the fuel oil composition of this disclosure are the same as those described later as being included in the fuel oil composition. The properties of these base materials, as well as the properties of the fuel oil composition obtained by the manufacturing method of this disclosure, are the same as those described later in the fuel oil composition of this disclosure. Moreover, the processing ratios of these base materials are the same as those described later in the fuel oil composition of this disclosure. Furthermore, the ability to mix various additives as needed is the same as described later in the fuel oil composition of this disclosure.

[0036] (Uses of fuel oil composition) The use of the fuel oil composition produced by the manufacturing method of this disclosure is not particularly limited, but it is preferably used as a diesel fuel composition. Furthermore, the fuel oil composition is preferably used when operating an internal combustion engine, and more preferably when operating a diesel engine.

[0037] [Fuel oil composition] The fuel oil composition of this disclosure is manufactured by the manufacturing method of this disclosure described above. The fuel oil composition of this disclosure is not particularly limited in its components, as long as the estimated value M of PM generation calculated by the above formula (1) is below a predetermined threshold, it may contain, for example, the components described below.

[0038] When the fuel oil composition of this disclosure is a diesel fuel composition, the base materials included in the fuel oil composition are, for example, straight-run diesel fuel (LGO), hydrogenated desulfurized diesel fuel (DGO), hydrodesulfurized kerosene (DK), hydrocracking kerosene (HCK), desulfurized heavy naphtha (DHN), light lubricating oil fraction (LL: fraction obtained by hydrogenating a fraction close to diesel fuel), hydrocracking diesel fuel (HCGO), cracked diesel fuel (LCO), light cracked diesel fuel (LLCO), pyrocrazed diesel fuel (CGO), pyrocrazed light diesel fuel (LCGO), dewaxed diesel fuel (DWGO), dewaxed and desulfurized diesel fuel (DWDGO), directly desulfurized diesel fuel (DSGO), indirectly desulfurized light diesel fuel (VH-LGO), high-boiling point heavy naphtha (HHN), fatty acid methyl ester (FAME), HBD (hydrogenated biofuel), HVO (hydrogenated vegetable oil), GTL (Gas To Examples include diesel fuel base materials produced by processes such as the Liquid (Liquid) and the Fischer-Tropsch process.

[0039] From the viewpoint of promoting the use of cracked substrates, the fuel oil composition of this disclosure preferably contains one or more selected from the group consisting of cracked light oil (LCO) and pyrolytic light light oil (LCGO). Generally, increasing the processing ratio of LCO tends to increase the aromatic content, and increasing the processing ratio of LCGO tends to increase the naphthenic content. However, by controlling the characteristics of the fuel oil composition based on the aforementioned formula (1), it is possible to increase the processing ratio of decomposition-type substrates such as LCO and LCGO while suppressing PM generation.

[0040] (Other additives) The fuel oil composition of this disclosure may, as necessary, contain various additives such as antioxidants, fluidity improvers, lubricity improvers, cetane number improvers, combustion accelerators, detergents, sludge dispersants, and antifungal agents, selected appropriately within the range that can maintain the estimated value M of PM generation calculated by formula (1) above.

[0041] (Characteristics of fuel oil composition) As described above, the fuel oil composition of this disclosure only needs to have an estimated value M of PM generation calculated by formula (1) that is below a predetermined threshold, but it is also preferable that it has the following characteristics.

[0042] (Estimated PM generation amount M) As previously mentioned, there are no particular restrictions on the threshold value M for the estimated amount of PM generated, but it can be set to, for example, 2.7 mg. In other words, the fuel oil composition in one aspect of this disclosure has an estimated PM generation amount M calculated by formula (1) of 2.7 mg or less.

[0043] (V AB , V NB , V PA , V N1 , V PN (T10, T90) V of the fuel oil composition of the present disclosure AB , V NB , V PA , V N1 , V PN T10 and T90 are not particularly limited as long as the estimated value M of the PM generation amount calculated by equation (1) is less than or equal to a predetermined threshold, and their respective preferred embodiments are as described above.

[0044] (Density at 15°C) The density of the fuel oil composition of this disclosure at 15°C is preferably 0.7900 g / cm³. 3 More preferably, 0.8000 g / cm³ 3 More preferably 0.8050 g / cm³ 3 The above applies, with a preferred upper limit of 0.8600 g / cm³. 3 More preferably, 0.8550 g / cm³ 3 More preferably, 0.8500 g / cm³ 3 The following applies: In this disclosure, the density at 15°C is a value measured in accordance with JIS K 2249-1:2011 (Crude oil and petroleum products - Method for determining density - Part 1: Vibration method).

[0045] (Kinematic viscosity at 30°C) The kinematic viscosity of the fuel oil composition of this disclosure at 30°C is preferably 2,000 mm². 2 / s or more, more preferably 2,200 mm 2 / s or more, more preferably 2,400 mm 2 The value is 1 / s or more, and preferably has an upper limit of 4.700 mm. 2 / s or less, more preferably 4,600 mm 2 / s or less, more preferably 4.550 mm 2 It is less than or equal to / s. In this disclosure, the kinematic viscosity at 30°C is a value measured in accordance with JIS K 2283:2000 (Test method for kinematic viscosity of crude oil and petroleum products).

[0046] (Cetane number) The cetane number of the fuel oil composition of this disclosure is preferably 47.5 or higher, more preferably 48.0 or higher, even more preferably 49.0 or higher, and even more preferably 50.0 or higher, with an upper limit of usually 75.0 or lower, preferably 70.0 or lower, more preferably 65.0 or lower, and even more preferably 60.0 or lower. In this disclosure, the cetane number is a value determined in accordance with JIS K 2280-4:2013 (Petroleum products - Method for determining octane number, cetane number and cetane index - Part 4: Cetane number).

[0047] (Cetane index) The cetane index of the fuel oil composition of this disclosure is preferably 47.5 or higher, more preferably 48.0 or higher, even more preferably 49.0 or higher, and even more preferably 50.0 or higher, with an upper limit of typically 75.0 or lower, and preferably 70.5 or lower. In this disclosure, the cetane index is a value determined in accordance with JIS K 2280-5:2013 (Petroleum products - Method for determining octane number, cetane number and cetane index - Part 5: Cetane index).

[0048] (Uses of fuel oil composition) The uses of the fuel oil composition of this disclosure are not particularly limited, but it is preferably used as a diesel fuel composition. Furthermore, the fuel oil composition is preferably used when operating an internal combustion engine, and more preferably when operating a diesel engine.

[0049] [Method for selecting fuel oil compositions] Using the PM generation estimation method of this disclosure, it is also possible to estimate the PM generation amount of the manufactured fuel oil composition and select only the fuel oil compositions that fall below a predetermined threshold from the manufactured fuel oil compositions. In other words, the fuel oil composition selection method of this disclosure is a fuel oil composition selection method that includes a step of selecting fuel oil compositions in which the estimated value M of the amount of PM generated when an internal combustion engine is operated using the fuel oil composition, represented by the formula (1) described above, is less than or equal to a preset threshold.

[0050] [One aspect of the disclosure provided] One aspect of this disclosure provides the following [1] to [9]. [1] A method for estimating the amount of PM generated during the operation of an internal combustion engine, based on the characteristics of the fuel oil composition used during the operation of the internal combustion engine, A method for estimating PM generation, which includes the step of calculating an estimated value of PM generation based on the following formula (1). M = 0.044 × V AB +0.065 × V NB +0.091 × V PA +0.017 × V N1 +0.040 × V PN +0.027×(T10-220)+0.018×(T90-330)+C...(1) However, in equation (1) above, M represents the estimated amount of PM produced [mg], and C is a predetermined arbitrary constant. Also, V AB , V NB , V PA , V N1 , and V PN These values ​​represent the content [volume %] of the following components based on the total amount (100 volume %) of the fuel oil composition. V AB : Alkylbenzene V NB : Naphthenobenzene V PA : 2 or more rings of aroma V N1 :1 ring naphthene V PN : Naphthenes of 2 or more rings Furthermore, T10 represents the 10% volume distillation temperature [°C] of the fuel oil composition, and T90 represents the 90% volume distillation temperature [°C] of the fuel oil composition. [2] The method for estimating PM generation amount according to [1], wherein the fuel oil composition is a diesel oil composition. [3] The method for estimating PM generation amount according to [1] or [2], wherein the internal combustion engine is a diesel engine. [4] A method for producing a fuel oil composition, A method for producing a fuel oil composition, comprising the step of controlling the composition of the fuel oil composition such that the estimated amount M of PM generated when an internal combustion engine is operated using the fuel oil composition, represented by the following formula (1), is less than or equal to a preset threshold. M = 0.044 × V AB+0.065 × V NB +0.091 × V PA +0.017 × V N1 +0.040 × V PN +0.027×(T10-220)+0.018×(T90-330)+C...(1) However, in equation (1) above, M represents the estimated amount of PM produced [mg], and C is a predetermined arbitrary constant. Also, V AB , V NB , V PA , V N1 , and V PN These values ​​represent the content [volume %] of the following components based on the total amount (100 volume %) of the fuel oil composition. V AB : Alkylbenzene V NB : Naphthenobenzene V PA : 2 or more rings of aroma V N1 :1 ring naphthene V PN : Naphthenes of 2 or more rings Furthermore, T10 represents the 10% volume distillation temperature [°C] of the fuel oil composition, and T90 represents the 90% volume distillation temperature [°C] of the fuel oil composition. [5] A method for producing a fuel oil composition according to [4], comprising the step of controlling the composition of the fuel oil composition so that the estimated value M is 2.7 mg or less. [6] A method for producing a fuel oil composition according to [4] or [5], wherein the fuel oil composition is a diesel fuel composition. [7] A method for producing a fuel oil composition according to any one of [4] to [6], wherein the internal combustion engine is a diesel engine. [8] A fuel oil composition manufactured by the manufacturing method described in any one of items [4] to [7]. [9] A fuel oil composition, A fuel oil composition in which the estimated amount M of PM generated when an internal combustion engine is operated using the fuel oil composition, as represented by the following formula (1), is 2.7 mg or less. M = 0.044 × V AB +0.065 × V NB +0.091 × V PA +0.017 × V N1 +0.040 × V PN +0.027×(T10-220)+0.018×(T90-330)+C...(1) However, in equation (1) above, M represents the estimated amount of PM produced [mg], and C is a predetermined arbitrary constant. Also, V AB , V NB , V PA , V N1 , and V PN These values ​​represent the content [volume %] of the following components based on the total amount (100 volume %) of the fuel oil composition. V AB : Alkylbenzene V NB : Naphthenobenzene V PA : 2 or more rings of aroma V N1 :1 ring naphthene V PN : Naphthenes of 2 or more rings Furthermore, T10 represents the 10% volume distillation temperature [°C] of the fuel oil composition, and T90 represents the 90% volume distillation temperature [°C] of the fuel oil composition. [Examples]

[0051] The present disclosure will be described in detail below with reference to examples, but the present disclosure is not limited in any way to these examples.

[0052] [Examples 1-19] Fuel oil compositions with the compositions shown in Tables 2 and 3 were prepared by mixing the following components having the characteristics shown in Table 1, and the evaluations described below were performed. The details of each component used in the preparation of the fuel oil compositions shown in Tables 2 and 3 are described below.

[0053] <Base material> • Straight-run diesel fuel

[0054] <Heavy aromatic solvent 1> • Swazole 1500 (manufactured by Maruzen Petrochemical Co., Ltd.)

[0055] <Heavy Aromatic Solvents 2> • Swazole 1800 (manufactured by Maruzen Petrochemical Co., Ltd.)

[0056] Hydrogenated Vegetable Oil (HVO) • The product used was obtained by hydrogenating vegetable oil or waste cooking oil. Generally, vegetable oils such as palm oil can be used, and waste cooking oils such as those discharged from the food industry can be used.

[0057] <Isoparaffin-based substrate 1> • IP Solvent 1620 (manufactured by Idemitsu Kosan Co., Ltd.)

[0058] <Isoparaffin-based substrate 2> • IP Solvent 2028 (manufactured by Idemitsu Kosan Co., Ltd.)

[0059] <Isoparaffin-based substrate 3> • IP Solvent 2835 (manufactured by Idemitsu Kosan Co., Ltd.)

[0060] <Naphthenic base material 1> • Naphthezol Grade 160 (manufactured by ENEOS Corporation)

[0061] <Naphthenic base material 2> • Naphthezol Grade 220 (manufactured by ENEOS Corporation)

[0062] <Naphthenic base material 3> • Exxon D110 (manufactured by ExxonMobil)

[0063] <Naphthenic base material 4> • Exxon D130 (manufactured by ExxonMobil)

[0064] <Naphthenobenzene-based substrate> • Tetralin (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0065] <Hydroxide-based substrates> • Normal cetane (manufactured by ENEOS Sun Energy Co., Ltd.)

[0066] <Bicyclic naphthenic substrate> • Decalin (manufactured by Fujifilm Wako Pure Chemical Industries, Ltd.)

[0067] <Bi-ring aroma-based base material> • 1-Methylnaphthalene (manufactured by Tokyo Chemical Industry Co., Ltd.)

[0068] <Kerosene> • Straight-run kerosene fraction

[0069] <Base material with heavy parts removed> The aforementioned base material was subjected to atmospheric pressure distillation and fractionation, and the fraction obtained up to a distillation temperature of 310°C was used.

[0070] <Base material A> • A mixture of straight-run diesel fuel with LCO and LCGO, described below, was used.

[0071] <Base material B> • A mixture of straight-run diesel fuel with LCO and LCGO, described below, was used.

[0072] <Base material C> • A mixture of straight-run diesel fuel with LCO and LCGO, described below, was used.

[0073] <Base material D> • A mixture of straight-run diesel fuel and LCGO (Low-Cold Gas Oxide), as described below, was used.

[0074] <Cracked diesel fuel (LCO)> • The oil used was obtained by decomposing atmospheric distillation residue oil using a fluid cracking apparatus. It is characterized by its high aromatic content.

[0075] <Pyrolytic Light Gas Oil (LCGO)> The oil used was obtained by thermally decomposing atmospheric distillation residue oil using a residual oil thermal decomposition apparatus. It is characterized by its high naphthene content.

[0076] [Comparative Examples 1-2] In Comparative Example 1, a mixture was used in which the aforementioned base material C was present in an amount of 97% by volume and the heavy aromatic solvent 2 was present in an amount of 3% by volume. In Comparative Example 2, a mixture was used in which the aforementioned base material C was present in an amount of 90% by volume and the heavy aromatic solvent 2 was present in an amount of 10% by volume.

[0077] [Various properties of fuel oil compositions] The properties of each raw material used in each example and comparative example, as well as the properties of the fuel oil compositions in each example and comparative example, were measured according to the procedure described below. The results are shown in Table 2.

[0078] <Content of each component (V AB , V NB , V PA , V N1 , V PN )> First, the saturated, unsaturated, mono-ring aromatic, di-ring aromatic, and tri-ring or more aromatic content of each fuel oil composition was measured according to the High Performance Liquid Chromatography method, as specified in JPI-5S-49-2007, which describes petroleum products - hydrocarbon type test methods. Subsequently, in accordance with ASTM D 2425 (Standard Test Method for Hydrocarbon Types in Middle Distillates by Mass Spectrometry), detailed analysis of naphthenes and aromatics (alkylbenzene, naphthenobenzene, etc.) was performed to determine the content of each component.

[0079] <10 volume% distillation temperature and 90 volume% distillation temperature (T10, T90)> The measurement was carried out in accordance with JIS K2254:2018 (Petroleum products - Determination of distillation characteristics - Atmospheric pressure method).

[0080] <Density at 15°C> The measurement was carried out in accordance with JIS K 2249-1:2011 (Crude petroleum and petroleum products - Determination of density - Part 1: Vibrating tube method).

[0081] <Kinematic viscosity at 30°C> The measurement was carried out in accordance with JIS K 2283:2000 (Testing method for kinematic viscosity of crude petroleum and petroleum products).

[0082] <Cetane number> The measurement was carried out in accordance with JIS K 2280-4:2013 (Petroleum products - Determination of octane number, cetane number and cetane index - Part 4: Cetane number).

[0083] <Cetane index> The measurement was carried out in accordance with JIS K 2280-5:2013 (Petroleum products - Determination of octane number, cetane number and cetane index - Part 5: Cetane index).

[0084] [Running test] Running tests using the fuel oil compositions of each example and each comparative example were carried out in accordance with the procedure shown below.

[0085] <Estimated PM value> V of each fuel oil composition AB , V NB , V PA , V N1 , V PN , the numerical values of T10 and T90 were substituted into the following formula to calculate the estimated PM value M. The constant term C was set to 0.29. The results are shown in Table 1 and Table 2. M=0.044×V AB +0.065×V NB +0.091×V PA +0.017×V N1 +0.040×V PN +0.027×(T10-220)+0.018×(T90-330)+C···(1)

[0086] <PM実測値> Using the fuel oil compositions shown in Examples 1 to 19, a running test was conducted under the following conditions. The results are shown in Table 2. (1) Engine specifications · Engine type: In-line 4-cylinder diesel · Displacement: 3.0 L · Maximum engine output: 110 kW / 2800 rpm · Maximum engine torque: 375 Nm / 1400~2800 rpm · Engine bore × stroke: 95.4 mm × 104.9 mm · Compression ratio: 15.8 · Regulation compliance: Compliant with the Post-New Long-Term Exhaust Gas Regulation (2) Running test Using a test vehicle with the specifications shown in (1), a running test was conducted at an intake air temperature of 25°C and a humidity of 50%, with the operation mode set to the JE05 mode specified in "Public Notice for Establishing Details of Safety Standards for Road Transport Vehicles [2008.03.25] Attachment 41 (Measurement Method for Heavy-duty Vehicle Exhaust Gas)" issued by the Ministry of Land, Infrastructure, Transport and Tourism. (3) Measurement of PM production amount In the above running test, a PM collection device ("Micro Tunnel MDLT-1300T" manufactured by Horiba, Ltd.) was connected to the exhaust pipe of the vehicle used, and the generated PM was collected by a collection filter ("TX40HI20-WW" manufactured by Tokyo Dylec Co., Ltd.). Then, the increase in mass of the collection filter after PM collection was defined as the PM production amount [mg]. The above test was repeated four times, and the average value of the last two tests is shown as the result.

[0087] <DPF再生インターバル、自動再生後のDOC差圧> Using the fuel oil compositions shown in Examples 15 to 17 and Comparative Examples 1 to 2, the aforementioned running test was repeatedly carried out. The differential pressure across the DOC was measured using a pressure sensor, and the point at which the differential pressure across the DOC reached its maximum during the JE05 mode operation cycle was extracted and plotted. The differential pressure across the DOC is the maximum value of the change in differential pressure across the DOC relative to that immediately after the start of the initial running test. During the repeated JE05 mode operation cycle, PM generated in the DPF and DOC accumulates, and the differential pressure gradually increases. When it exceeds a certain threshold, the DPF is automatically regenerated to clear the PM buildup. The driving test was repeated until the DPF automatic regeneration was performed twice. The DOC differential pressure immediately after the start of the driving test after the second automatic regeneration was defined as the DOC differential pressure after automatic regeneration. In addition, the number of JE05 mode cycles that could be run until the first automatic regeneration occurred, and from the first automatic regeneration until the second automatic regeneration occurred (hereinafter also referred to as the 1st cycle DPF regeneration interval and the 2nd cycle DPF regeneration interval), were measured, and these two points were used as evaluation items. The results are shown in Table 3.

[0088] [Table 1]

[0089] [Table 2]

[0090] [Table 3]

[0091] From Table 2, the following can be seen. A simple linear regression analysis was performed on the fuel oil compositions of Examples 1 to 19, with the estimated PM generation amount as the explanatory variable and the measured PM generation amount as the dependent variable. The coefficient of determination was 0.90, indicating that the estimation formula in this disclosure can estimate PM generation with high accuracy. Furthermore, the following can be seen from Table 3. The fuel oil compositions of Examples 15-17, whose PM estimate value according to formula (1) is 2.7 mg or less, exhibit low DOC differential pressure after automatic regeneration. On the other hand, the fuel oil compositions of Comparative Examples 1 and 2, in which the estimated PM value according to formula (1) was greater than 2.7 mg, had a short DPF regeneration interval and a high DOC differential pressure after automatic regeneration. Furthermore, even after two automatic DPF regenerations, forced regeneration was performed, but the PM could not be sufficiently removed, resulting in a problem where the DOC differential pressure did not decrease. Therefore, it can be seen that the threshold at which DOC performance deteriorates can be set, for example, when the PM estimate using equation (1) is 2.7 mg or less.

Claims

1. A method for estimating the amount of PM generated during the operation of an internal combustion engine, based on the characteristics of the fuel oil composition used during the operation of the internal combustion engine, A method for estimating PM generation, comprising the step of calculating an estimated value of PM generation amount based on the following formula (1). M=0.044×V ＡＢ +0.065×V ＮＢ +0.091×V ＰＡ +0.017×V Ｎ１ +0.040×V ＰＮ +0.027×(T10-220)+0.018×(T90-330)+C・・・(1) However, in equation (1) above, M represents the estimated amount of PM generated [mg], and C is a predetermined arbitrary constant. Further, V ＡＢ , V ＮＢ , V ＰＡ , V Ｎ１ , and V ＰＮ each represent the content [volume%] of the following components based on the total amount (100 volume%) of the fuel oil composition. V ＡＢ : Alkylbenzene V ＮＢ : Naphthenobenzene V ＰＡ : Aroma components of 2 or more rings V Ｎ１ : 1-ring naphthene V ＰＮ : Naphthenes with 2 or more rings Furthermore, T10 represents the 10% by volume distillation temperature [°C] of the fuel oil composition, and T90 represents the 90% by volume distillation temperature [°C] of the fuel oil composition.

2. The method for estimating PM generation amount according to claim 1, wherein the fuel oil composition is a diesel fuel composition.

3. The method for estimating PM generation amount according to claim 1 or 2, wherein the internal combustion engine is a diesel engine.

4. A method for producing a fuel oil composition, A method for producing a fuel oil composition, comprising the step of controlling the composition of the fuel oil composition such that the estimated amount M of PM generated when an internal combustion engine is operated using the fuel oil composition, represented by the following formula (1), is less than or equal to a preset threshold. M=0.044×V ＡＢ +0.065×V ＮＢ +0.091×V ＰＡ +0.017×V Ｎ１ +0.040×V ＰＮ +0.027×(T10-220)+0.018×(T90-330)+C・・・(1) However, in equation (1) above, M represents the estimated amount of PM generated [mg], and C is a predetermined arbitrary constant. Also, V ＡＢ , V ＮＢ , V ＰＡ , V Ｎ１ , and V ＰＮ These values ​​represent the content [volume %] of the following components based on the total amount (100 volume %) of the fuel oil composition. V ＡＢ : Alkylbenzene V ＮＢ : Naphthenobenzene V ＰＡ : Aroma components of 2 or more rings V Ｎ１ : 1-ring naphthene V ＰＮ : Naphthenes with 2 or more rings Furthermore, T10 represents the 10% by volume distillation temperature [°C] of the fuel oil composition, and T90 represents the 90% by volume distillation temperature [°C] of the fuel oil composition.

5. A method for producing a fuel oil composition according to claim 4, comprising the step of controlling the composition of the fuel oil composition such that the estimated value M is 2.7 mg or less.

6. The method for producing a fuel oil composition according to claim 4 or 5, wherein the fuel oil composition is a diesel fuel composition.

7. A method for producing a fuel oil composition according to any one of claims 4 to 6, wherein the internal combustion engine is a diesel engine.

8. A fuel oil composition manufactured by the manufacturing method described in any one of claims 4 to 7.

9. A fuel oil composition, A fuel oil composition in which the estimated amount M of PM generated when an internal combustion engine is operated using the fuel oil composition, as shown in the following formula (1), is 2.7 mg or less. M=0.044×V ＡＢ +0.065×V ＮＢ +0.091×V ＰＡ +0.017×V Ｎ１ +0.040×V ＰＮ +0.027×(T10-220)+0.018×(T90-330)+C・・・(1) However, in equation (1) above, M represents the estimated amount of PM generated [mg], and C is a predetermined arbitrary constant. Also, V ＡＢ , V ＮＢ , V ＰＡ , V Ｎ１ , and V ＰＮ These values ​​represent the content [volume %] of the following components based on the total amount (100 volume %) of the fuel oil composition. V ＡＢ : Alkylbenzene V ＮＢ : Naphthenobenzene V ＰＡ : Aroma components of 2 or more rings V Ｎ１ : 1-ring naphthene V ＰＮ : Naphthenes with 2 or more rings Furthermore, T10 represents the 10% by volume distillation temperature [°C] of the fuel oil composition, and T90 represents the 90% by volume distillation temperature [°C] of the fuel oil composition.

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