A Heavy Oil Composition
Isoparaffin-based heavy oil compositions using biomass-derived materials achieve low-temperature fluidity and compliance with environmental standards by optimizing sulfur, isoparaffin, and n-paraffin contents, addressing the need for cold flow improvers in conventional heavy oil compositions.
Patent Information
- Authority / Receiving Office
- JP · JP
- Patent Type
- Patents
- Current Assignee / Owner
- Filing Date
- 2022-08-31
- Publication Date
- 2026-03-11
AI Technical Summary
There is a growing demand for heavy oil compositions containing biomass as a main blending component that exhibit excellent low-temperature fluidity without the addition of a cold flow improver, which conventional compositions lack.
Utilizing isoparaffin-based base materials derived from renewable raw materials, such as animal and vegetable oils, as a carbon residue adjuster in heavy oil compositions, along with specific composition ranges for sulfur, isoparaffin, n-paraffin, and aromatic contents, to achieve low-temperature fluidity without a cold flow improver.
The resulting heavy oil composition exhibits excellent low-temperature fluidity and meets environmental and tax regulations, reducing the need for additives and minimizing wax crystal formation in fuel filters.
Smart Images

Figure 0007828260000001 
Figure 0007828260000002 
Figure 0007828260000003
Abstract
Description
[Technical Field]
[0001] The present invention relates to a heavy oil composition A. [Background technology]
[0002] Heavy oil compositions have traditionally been used for a variety of purposes in various industrial fields, and are classified into three types according to kinematic viscosity in JIS K2205: Type 1 (heavy oil A), Type 2 (heavy oil B), and Type 3 (heavy oil C). Of these heavy oil compositions, heavy oil A (heavy oil composition A) is used as fuel oil for heaters for greenhouse heating, heaters for buildings, and fuel oil for fishing boats.
[0003] In general, a heavy oil composition A contains one or more middle distillate base stocks selected from straight-run kerosene or desulfurized kerosene obtained from an atmospheric distillation unit, straight-run light diesel oil or desulfurized straight-run light diesel oil, light cycle oil obtained from a fluid catalytic cracking unit, and directly desulfurized light diesel oil obtained from a direct desulfurization unit, and further contains residual oils such as atmospheric distillation residual oil, vacuum distillation residual oil, directly desulfurized residual oil, and extract oil (a by-product oil obtained by solvent extraction of lubricating oil) as a carbon residue adjuster (carbon residue imparting base stock).
[0004] Regarding the residual carbon content of heavy oil composition A, JIS K 2205 (heavy oil) specifies that it must be 4 mass% or less. In addition, in order to clarify the product classification from light oil composition and to avoid being subject to light oil transaction tax, heavy oil composition A must contain a residual carbon content of 0.20 mass% or more of 10% residual oil.
[0005] Incidentally, engines and various combustion appliances that use heavy oil composition A as fuel are equipped with filters with mesh sizes of approximately 5 to 250 μm in the fuel system, etc., which remove foreign matter from the fuel oil and thereby protect the precision equipment downstream. However, it is known that when the oil temperature drops in winter, high-carbon-number n-paraffins (high-carbon-number linear saturated hydrocarbons) precipitate as wax crystals (sludge) and clog the above-mentioned filters.
[0006] Therefore, in order to suppress clogging of fuel filters due to the deposition of the above-mentioned wax crystals (sludge), for example, Patent Document 1 proposes adding a cold flow improver (CFI) to a heavy oil composition A to inhibit the growth of wax crystals and refine the wax crystals that are formed. [Prior art documents] [Patent documents]
[0007] [Patent Document 1] Japanese Patent Application Laid-Open No. 2003-292977 DISCLOSURE OF THE INVENTION [Problem to be solved by the invention]
[0008] On the other hand, in recent years, with the increase in environmental awareness, from the viewpoint of so-called carbon neutrality, etc., fuel oils using renewable raw materials, i.e., fuel oils using renewable raw materials containing base materials produced from organic resources derived from living organisms (biomass) by fermentation, oil extraction, pyrolysis, etc., have been attracting attention as an alternative to fossil fuels.
[0009] There is a growing demand for heavy oil compositions A that contain biomass or base materials made from biomass as the main blending component, but such heavy oil compositions A have been little known until now, and in addition, like conventional heavy oil compositions A, they require the addition of a cold flow improver (CFI).
[0010] Under these circumstances, an object of the present invention is to provide an A heavy oil composition that can be composed solely of biomass or a base material made from biomass as a raw material and that can exhibit excellent low-temperature fluidity without the addition of a cold flow improver (CFI). [Means for solving the problem]
[0011] Under these circumstances, the present inventors have come to focus on isoparaffin-based base materials among biomass or base materials made from biomass as a raw material.
[0012] In other words, fuel oil base stocks using renewable raw materials are known to be obtained through production methods involving synthesis reactions and isomerization reactions, but such fuel oil base stocks are composed mostly of branched-chain saturated hydrocarbons (isoparaffins), and the idea was conceived of using them as isoparaffin-based base stocks in the preparation of heavy oil composition A. The present inventors have found that by using animal and vegetable oils derived from renewable raw materials as a carbon residue adjuster together with the isoparaffin-based base material, excellent low-temperature fluidity can be exhibited without adding a cold flow improver (CFI), and have completed the present invention based on this finding.
[0013] That is, the present invention is The sulfur content is less than 10 ppm by mass, the isoparaffin content is 85.0% by volume or more, the n-paraffin content is 7.0% by mass or less, the aromatic content is 0.5% by volume or less, and the density at 15°C is 0.7900 to 0.8200 g / cm 3 , containing 65.0% by volume to 96.5% by volume of an isoparaffinic base material having a distillation range of 160.0 ° C to 480.0 ° C according to the specification of ASTM D 6352, Contains 3.5 to 35.0% by volume of animal and vegetable oils and fats, Residual carbon content in 10% residual oil is 0.20% by mass or more, Kinematic viscosity at 50°C is 10,000mm 2 / sec or less A heavy oil composition characterized by This provides: [Effects of the Invention]
[0014] According to the present invention, it is possible to provide an A heavy oil composition that can be composed exclusively of biomass or a base material made from biomass as a raw material and that can exhibit excellent low-temperature fluidity without the addition of a cold flow improver (CFI). DETAILED DESCRIPTION OF THE INVENTION
[0015] Hereinafter, embodiments of the present invention will be described in detail. In this specification, the use of "to" to indicate a range of values indicates a range that includes the values stated as the upper and lower limits. When a unit is stated for only the upper limit of a range of values expressed by "to," this means that the lower limit is also expressed in the same unit. In the numerical ranges described in stages in this specification, the upper or lower limit value described in one numerical range may be replaced with the upper or lower limit value of another numerical range described in stages. In this specification, the content or amount of each component in a composition means, unless otherwise specified, the total content or amount of the multiple substances present in the composition when multiple substances corresponding to each component are present in the composition. As used herein, combinations of preferred embodiments are more preferred embodiments.
[0016] In this specification, unless otherwise specified, the values of the following items are values determined using the following test methods and calculations. - "Isoparaffin content" The isoparaffin content means the value obtained by subtracting the n-paraffin (straight-chain saturated hydrocarbon) content calculated per volume by the method described below from the alkane (saturated chain hydrocarbon) content determined by the method described below. - "Alkane (chain saturated hydrocarbon) content and naphthene (cyclic saturated hydrocarbon) content" (1) Using high performance liquid chromatography (HPLC), the saturated fraction (saturated hydrocarbon compounds) is separated under the following conditions. Measurement equipment: Shimadzu Corporation HPLC Column: Develosil 30-3 (4.6mm x 250mm) Mobile phase: n-hexane 1.0 mL / min 5.3 MPa Detector: CH1: UV254nm, CH2: RI Sample concentration: Dilute with n-hexane to approximately 20 vol.% Injection volume: 60μL Fractionation conditions: After elution of the saturated fraction, backflush is performed to elute the aromatic fraction all at once. (2) For the saturated fraction obtained in (1) above, an average mass spectrum is obtained using a gas chromatograph mass spectrometer (GC / MS) under the following conditions: Measuring device: Agilent GC-MS Column: DB-1HT 30m x 0.32mm I.D. x 0.10um Oven temperature: 40℃ (2 min) - (20℃ / min) - 300℃ (5 min) Run 20 min Carrier gas: He Constant pressure mode 30kPa Initial: 2.1mL / min, 52cm / sec Ionization voltage: EI 70eV Injection method: On-column injection Next, the volume ratio of alkanes and the volume ratio of naphthenes are calculated by substituting these values into the calculation formulas described in ASTM D 2786, and the content of alkanes and the content of naphthenes relative to the entire solution are calculated by multiplying the value of the saturated content (volume %) measured in accordance with JPI-5S-49-07 "Petroleum Products - Hydrocarbon Type Test Method - High Performance Liquid Chromatography" described below by the calculated volume ratios. In addition, the factors used for calculation in ASTM D 2786 were an average carbon number of 16 and n-paraffin as the calculation factor. "Method for measuring n-paraffin content" The n-paraffin content refers to a value measured and calculated under the conditions described below, and unless otherwise specified, refers to the content of n-paraffins having 9 or more carbon atoms. Measuring device: Agilent GC-FID Column: DB-1 60m x 0.32mm ID DF: 0.25μm Measurement start temperature (holding time): 60℃ (5min) Measurement end temperature (holding time): 340℃ (14min) Oven temperature rise rate: 6℃ / min Carrier gas: He 152kPa FID combustion gas: H230mK / min, Air 400mL / min Quantitative method: Internal standard method (di-n-butyl phthalate) Sample dilution: toluene Injection method: On-column injection The n-paraffin content converted per volume means the value obtained by dividing the n-paraffin content measured by the above method by 0.75. ·"Saturate content" This refers to the value measured by the method described in JPI-5S-49-07 "Petroleum Products - Hydrocarbon Type Testing Method - High Performance Liquid Chromatography." "Olefin content" This refers to the value measured by the method described in JPI-5S-49-07 "Petroleum Products - Hydrocarbon Type Testing Method - High Performance Liquid Chromatography." ·"Aromatic content" The aromatic content refers to the value measured by the method described in JPI-5S-49-07 "Petroleum products - Hydrocarbon type testing method - High performance liquid chromatography method." However, the aromatic content of the feedstock oil used for high-pressure hydrotreating and the aromatic content used in the calorific value measurement described below refer to values measured according to IP548 "Determination of aromatic hydrocarbon types in middle distillates - High performance liquid chromatography method With refractive index detection." ·“Distillation properties (distillation temperature)” Isoparaffinic base stock and heavy oil composition A containing an isoparaffinic base stock: Gas chromatographic distillation test method specified in ASTM D6352. Petroleum-based base materials other than isoparaffin-based base materials: The method specified in the "Atmospheric pressure distillation test method" specified in JIS K 2254:1998 "Petroleum products - Distillation test method." "10% residual carbon content of residual oil" This is the method specified in JIS K 2270-2:2009 "Crude oil and petroleum products - Determination of residual carbon content - Part 2: Micro method." "Kinematic viscosity at 50°C (Kinematic viscosity (50°C))" This is the method specified in JIS K 2283:2000 "Crude oil and petroleum products - Kinematic viscosity test method and viscosity index calculation method." "Density at 15°C (Density (15°C))" This is the method specified in JIS K 2249-1:2011 "Crude oil and petroleum products - Determination of density - (Vibration method)". "Sulfur content" Sulfur content of 500 mass ppm or less: Method specified in JIS K 2541-6:2003 "Crude oil and petroleum products - Determination of sulfur content - Part 6: Ultraviolet fluorescence method." Sulfur content exceeding 500 ppm by mass: Method specified in JIS K 2541-4:2003 "Crude oil and petroleum products - Determination of sulfur content - Part 4: Radiation excitation method." ·"ash" A method specified in JIS K2272. ·"moisture" Karl Fischer coulometric titration method described in JIS K 2275-3 "Crude oil and petroleum products - Testing method for moisture content." ·"reaction" The method specified in JIS K 2252 (1998) "Petroleum products - Reactivity test method." ·"flash point" The method specified in JIS K 2265-3:2007 "Determination of flash point - Part 3: Pensky-Martens closed-cell method" (PM method). ·“Pour point (PP)” The method specified in JIS K 2269:1987 "Test method for pour point and cloud point of crude oil and petroleum products." "Sludge volume" After measuring the weight of the membrane filter (pore size 1.2 μm) to the nearest 0.1 mg, set the membrane filter in a vacuum filtration device and filter 100 mL of the measurement sample. After no liquid is visible on the membrane filter, wash it with n-heptane until no oily substance is visible on the edge of the membrane filter. Then, dry the membrane filter under reduced pressure, measure the weight of the membrane filter after drying, and subtract the weight of the filter from the weight of the membrane filter after drying to calculate the sludge volume. "Cetane index" A method specified in JIS K 2204:1992.
[0017] The heavy oil composition A according to the present invention comprises: The sulfur content is less than 10 ppm by mass, the isoparaffin content is 85.0% by volume or more, the n-paraffin content is 7.0% by mass or less, the aromatic content is 0.5% by volume or less, and the density at 15°C is 0.7900 to 0.8200 g / cm 3 , containing 65.0% by volume to 96.5% by volume of an isoparaffinic base material having a distillation range of 160.0 ° C to 480.0 ° C according to the specification of ASTM D 6352, Contains 3.5 to 35.0% by volume of animal and vegetable oils and fats, Residual carbon content in 10% residual oil is 0.20% by mass or more, Kinematic viscosity at 50°C is 10,000mm 2 / sec or less It is characterized by the following.
[0018] Each of the base materials constituting the fuel oil composition A according to the present invention will be explained below.
[0019] The A fuel oil composition according to the present invention contains an isoparaffinic base stock as a constituent base stock, and the isoparaffinic base stock can be obtained using biomass as a raw material.
[0020] The isoparaffinic base stock constituting the A heavy oil composition according to the present invention has a sulfur content of less than 10 ppm by mass (0 ppm by mass or more and less than 10 ppm by mass), preferably 5 ppm by mass or less (0 ppm by mass or more and 5 ppm by mass or less), and more preferably 1 ppm by mass or less (0 ppm by mass or more and 1 ppm by mass or less). When the sulfur content of the isoparaffinic base material constituting the A fuel oil composition of the present invention is within the above range, the production of sulfur oxides during combustion can be easily reduced.
[0021] The isoparaffinic base material constituting the A heavy oil composition according to the present invention has an isoparaffin (branched saturated hydrocarbon) content of 85.0% by volume or more (85.0 to 100.0% by volume), preferably 88.0% by volume or more (88.0 to 100.0% by volume), and more preferably 91.0% by volume or more (91.0 to 100.0% by volume).
[0022] The isoparaffinic base material constituting the A heavy oil composition according to the present invention has an n-paraffin (straight-chain saturated hydrocarbon) content of 7.0 mass% or less (0.0 mass% to 7.0 mass%), preferably 6.0 mass% or less (0.0 mass% to 6.0 mass%), and more preferably 5.0 mass% or less (0.0 mass% to 5.0 mass%).
[0023] The isoparaffinic base material constituting the A heavy oil composition according to the present invention preferably has an alkane (chain saturated hydrocarbon) content of 84.0% by volume or more (84.0% by volume to 100.0% by volume), more preferably 87.0% by volume or more (87.0% by volume to 100.0% by volume), and even more preferably 90.0% by volume or more (90.0% by volume to 100.0% by volume).
[0024] The isoparaffinic base material constituting the A heavy oil composition according to the present invention has a saturated component (saturated hydrocarbon compound) content of 99.0% by volume or more (99.0% by volume to 100.0% by volume), preferably 99.2% by volume or more (99.2% by volume to 100.0% by volume), and more preferably 99.4% by volume or more (99.4% by volume to 100.0% by volume).
[0025] The isoparaffinic base material constituting the heavy-containing composition A according to the present invention preferably has an olefin content of 0.5% by volume or less (0.0% by volume to 0.5% by volume), more preferably 0.4% by volume or less (0.0% by volume to 0.4% by volume), and even more preferably 0.3% by volume or less (0.0% by volume to 0.3% by volume).
[0026] The isoparaffinic base material constituting the A heavy oil composition according to the present invention has an aromatic content (aromatic hydrocarbon compound) of 0.5% by volume or less (0.0% by volume to 0.5% by volume), preferably 0.4% by volume or less (0.0% by volume to 0.4% by volume), and more preferably 0.3% by volume or less (0.0% by volume to 0.3% by volume).
[0027] In the isoparaffinic base stock that constitutes the A heavy oil composition of the present invention, the isoparaffin content, n-paraffin content, and aromatic content are all within the above-mentioned ranges, and the majority of the content is made up of isoparaffins, with a low content of n-paraffins, which tend to generate wax, so that when blended into the A heavy oil composition, the pour point can be easily lowered.
[0028] The isoparaffinic base material constituting the A heavy oil composition according to the present invention has a density at 15°C of 0.7900 to 0.8200 g / cm 3 and 0.7930 g / cm 3 ~0.8180g / cm 3 Preferably, it is 0.7950 g / cm 3 ~0.8150g / cm 3 It is more preferable that: When the density of the isoparaffinic base material constituting the A fuel oil composition according to the present invention is within the above range, a good combustion state can be easily achieved when the A fuel oil composition is combusted.
[0029] The isoparaffinic base stock constituting the A heavy oil composition according to the present invention has a distillation range of 160°C to 480°C, preferably 165°C to 470°C, and more preferably 170°C to 460°C. By ensuring that the distillation range of the isoparaffinic base material constituting the A heavy oil composition of the present invention is within the above range, when the A heavy oil composition is prepared, it is possible to impart distillation properties suitable for each application. In the present application, the distillation range means the range from the initial boiling point (IBP) to the end point (EP) when a gas chromatograph distillation test is performed according to the ASTM D6352 standard, with the 0.5% by volume distillation temperature as the initial boiling point (IBP) and the 99.5% by volume distillation temperature as the end point (EP).
[0030] The isoparaffinic base stock constituting the A heavy oil composition according to the present invention is preferably one having an initial boiling point (IBP) of 160 to 200°C, more preferably 165 to 195°C, and even more preferably 170 to 190°C, when a gas chromatographic distillation test is carried out in accordance with the provisions of ASTM D6352 and the 0.5% by volume distillation temperature is taken as the initial boiling point (IBP). The isoparaffinic base material constituting the A heavy oil composition according to the present invention preferably has a 10% by volume distillation temperature (T10) of 190 to 250°C, more preferably 195 to 245°C, and even more preferably 200 to 250°C, when subjected to a gas chromatographic distillation test according to the ASTM D6352 standard. The isoparaffinic base material constituting the A heavy oil composition according to the present invention preferably has a 50% by volume distillation temperature (T50) of 230 to 310°C, more preferably 235 to 305°C, and even more preferably 240 to 300°C, when subjected to a gas chromatographic distillation test according to the ASTM D6352 standard. The isoparaffinic base material constituting the A heavy oil composition according to the present invention preferably has a 90% by volume distillation temperature (T90) of 290 to 380°C, more preferably 295 to 375°C, and even more preferably 300 to 370°C, when subjected to a gas chromatographic distillation test according to the ASTM D6352 standard. The isoparaffinic base material constituting the A heavy oil composition according to the present invention is preferably one having an end point (EP) of 400 to 470°C, more preferably 405 to 465°C, and even more preferably 410 to 460°C, when a gas chromatograph distillation test is carried out in accordance with the ASTM D6352 standard and the 99.5% by volume distillation temperature is used as the end point (EP).
[0031] The isoparaffinic base material constituting the A heavy oil composition of the present invention has IBP, T10, T50, T90 and EP within the above ranges, so that when used as a base material for fuel oil for heaters, fuel oil for ships, etc., it is possible to easily suppress deposit formation and deterioration of exhaust gas properties while maintaining appropriate spray and combustion conditions.
[0032] The isoparaffinic base material constituting the A heavy oil composition according to the present invention preferably has a flash point of 60.0°C or higher, more preferably 70.0°C or higher, and even more preferably 80.0°C or higher. Although there is no particular upper limit to the flash point of the isoparaffinic base material, the flash point of the isoparaffinic base material is usually 90.0°C or lower. If the flash point of the isoparaffinic base material constituting the A heavy oil composition of the present invention is within the above range, handling becomes easier.
[0033] The isoparaffinic base material constituting the A heavy oil composition according to the present invention preferably has a sludge amount of 0.0 to 1.0 mg / l, more preferably 0.0 to 0.7 mg / l, and even more preferably 0.0 to 0.5 mg / l. By ensuring that the amount of sludge produced that constitutes the isoparaffinic base material is within the above range, clogging of the filter can be made less likely when blended into an A heavy oil composition.
[0034] As the isoparaffinic base material constituting the A heavy oil composition according to the present invention, various base materials derived from biomass can be used.
[0035] The biomass-derived isoparaffinic base material is preferably one produced using lipids as a raw material, one synthesized using bioalcohol as a raw material, or one obtained by FT (Fischer-Tropsch) synthesis of biomass-derived synthesis gas. Specific examples of isoparaffin-based base materials produced using lipids as raw materials include those obtained by hydrogenating various lipids derived from waste cooking oil or general animal and vegetable oils, removing impurities, and then isomerizing the resulting paraffin content and subjecting it to appropriate fractional distillation. Furthermore, specific examples of isoparaffin-based base materials synthesized using bioalcohol as a raw material include those obtained by dehydrating ethanol or isobutanol produced by fermentation to produce ethylene or isobutene, which are then polymerized to form oligomers, and then subjected to appropriate fractional distillation treatment. Furthermore, examples of isoparaffin-based base materials produced by FT synthesis of biomass-derived synthesis gas include those produced by pyrolyzing and gasifying biomass using a pyrolysis furnace, and then subjecting the resulting synthesis gas to FT synthesis. In this application, bioalcohol refers to alcohols such as ethanol and butanol obtained by fermenting biomass and then subjecting it to appropriate filtration.
[0036] At least a portion of the isoparaffinic base stock constituting the A heavy oil composition according to the present invention may be an isoparaffinic base stock derived from petroleum. Examples of petroleum-derived isoparaffinic base stocks include fractions obtained in petroleum refining processes and fractions obtained by further synthesizing or isomerizing fractions obtained in petroleum refining processes, specifically fractions synthesized from isobutene, etc. obtained in petroleum refining processes. The isoparaffinic base material constituting the A heavy oil composition according to the present invention is preferably composed solely of base materials derived from biomass.
[0037] The A fuel oil composition according to the present invention contains the isoparaffinic base stock in an amount of 65.0 to 96.5% by volume, preferably 66.0 to 95.0% by volume, and more preferably 68.0 to 93.0% by volume.
[0038] The heavy oil composition A according to the present invention contains the above-mentioned isoparaffinic base material as the main base material in the above-mentioned proportions, and therefore can be composed of a base material made from biomass as a raw material, and can easily exhibit excellent low-temperature fluidity.
[0039] The fuel oil composition A according to the present invention contains an isoparaffinic base material and animal and vegetable oils and fats.
[0040] In the A fuel oil composition according to the present invention, the animal and vegetable oils and fats are not particularly limited as long as they are liquid at room temperature (20° C.) and can be blended into the A fuel oil composition.
[0041] The animal and vegetable oils contained in the A fuel oil composition of the present invention refer to oils and fats extracted from the fatty tissues of animals or oils and fats extracted from plants. The animal and vegetable fats and oils contained in the heavy oil composition A of the present invention are mainly composed of triacylglycerides consisting of fatty acids and glycerin, and may also contain other components such as mono- and diacylglycerides, vitamins, cholesterol, tocopherol, and plant sterols.
[0042] The raw material of the animal fat is not particularly limited, and examples thereof include one or more selected from beef tallow, milk lipids (butter), lamb oil, sheep oil, whale oil, fish oil, liver oil, horse oil, chicken oil, and the like.
[0043] The raw material of the vegetable oil is not particularly limited, and examples thereof include one or more selected from coconut, palm, olive, palm, soybean, rapeseed, sunflower, sesame, safflower, peanut, cottonseed, rice bran, corn, etc.
[0044] The animal and vegetable oils contained in the A fuel oil composition of the present invention are preferably vegetable oils, and specific examples thereof include one or more selected from palm oil, rapeseed oil, sunflower oil, soybean oil, and the like.
[0045] In the fuel oil composition A of the present invention, the animal and vegetable oil is a blending material made from biomass, which has excellent combustibility, and can be suitably blended as a carbon residue adjusting material (carbon residue imparting base material).
[0046] The A fuel oil composition according to the present invention contains the above animal and vegetable oils in an amount of 3.5 to 35.0% by volume, preferably 3.8 to 33.0% by volume, and more preferably 4.0 to 32.0% by volume.
[0047] The heavy oil composition A of the present invention contains animal and vegetable oils in the above proportions, and therefore exhibits excellent combustibility while also functioning suitably as a carbon residue adjuster (carbon residue imparting base material). In the heavy oil composition A of the present invention, if the blending ratio of the above-mentioned animal and vegetable oils is less than 3.5% by volume, the residual carbon content in the 10% residual oil will be less than 0.20% by mass, and the heavy oil composition A will not satisfy the tax law requirements. In the A heavy oil composition according to the present invention, if the blending ratio of the animal and vegetable oils exceeds 35.0% by volume, the kinematic viscosity at 50°C will be 10,000 mm 2 / sec, which requires heating in winter, and heating tends to reduce the oxidation stability of the A heavy oil composition.
[0048] The heavy oil composition A according to the present invention preferably has a total content of the above-mentioned isoparaffinic base material and animal and vegetable oils and fats of 90.0 to 100.0% by volume, more preferably 95.0 to 100.0% by volume, and even more preferably 98.0 to 100.0% by volume. The heavy oil composition A according to the present invention contains the isoparaffinic base material and animal and vegetable oils and fats in the above total proportions, so that the composition can be composed exclusively of biomass or a base material made from biomass as a raw material, It can easily exhibit excellent low-temperature fluidity without adding a cold flow improver (CFI).
[0049] When the A heavy oil composition according to the present invention contains a base material other than the above-mentioned isoparaffinic base material and animal and vegetable oils and fats, the isoparaffinic base material and the base material other than animal and vegetable oils and fats can be one or more selected from kerosene fractions, light oil fractions, petroleum residue fractions, etc.
[0050] The heavy oil composition A according to the present invention has a residual carbon content of 10% residual oil of 0.20 mass% or more, preferably 0.20 mass% to 1.00 mass%, more preferably 0.20 mass% to 0.90 mass%, and even more preferably 0.20 mass% to 0.80 mass%. By ensuring that the residual carbon content of the 10% residual oil of the A heavy oil composition according to the present invention is within the above range, it is possible to satisfies tax regulations and to suitably suppress sludge formation.
[0051] The heavy oil composition A according to the present invention has a kinematic viscosity at 50°C of 10,000 mm 2 / second or less (0.000~10.000mm 2 / sec) and 9.500mm 2 / second or less (0.000~9.500mm 2 / sec), and 9,400 mm 2 / second or less (0.000~9.400mm 2 / sec) is more preferable.
[0052] When the kinematic viscosity at 50°C of the A heavy oil composition of the present invention is within the above range, heating treatment in winter is not required and the decrease in oxidation stability that accompanies heating treatment can be suppressed.
[0053] The heavy oil composition A according to the present invention has a density of 0.8100 g / cm at 15°C. 3 ~0.8900g / cm 3 Preferably, it is 0.8120 g / cm 3 ~0.8880g / cm 3 More preferably, it is 0.8140 g / cm 3 ~0.8860g / cm 3 It is more preferable that: When the density of the A fuel oil composition at 15°C is within the above range, good combustion conditions can be easily achieved when the A fuel oil composition is combusted.
[0054] The fuel oil composition A according to the present invention preferably has a sulfur content of 1.20 mass% or less (0.00 mass% to 1.20 mass%), more preferably 1.10 mass% or less (0.00 mass% to 1.10 mass%), and even more preferably 1.00 mass% or less (0.00 mass% to 1.00 mass%). By ensuring that the sulfur content of the fuel oil composition A according to the present invention is within the above range, the sulfur content of the fuel oil composition A according to the present invention can be easily controlled within an appropriate range, making it possible to easily suppress the production of sulfur compounds during combustion.
[0055] The heavy oil composition A according to the present invention preferably has a 10.0% by volume distillation temperature of 190°C to 250°C, more preferably 195°C to 245°C, and even more preferably 200°C to 240°C, when subjected to a gas chromatographic distillation test according to the ASTM D6352 standard.
[0056] The heavy oil composition A according to the present invention preferably has a 50.0% by volume distillation temperature of 230°C to 310°C, more preferably 235°C to 305°C, and even more preferably 240°C to 300°C, when subjected to a gas chromatographic distillation test according to the ASTM D6352 standard.
[0057] The heavy oil composition A according to the present invention preferably has a 90.0% by volume distillation temperature of 290°C to 380°C, more preferably 295°C to 375°C, and even more preferably 300°C to 370°C, when subjected to a gas chromatographic distillation test according to the ASTM D6352 standard.
[0058] In the A fuel oil composition according to the present invention, the reaction is preferably neutral. In this application, the term "reaction" refers to a reaction test to determine whether or not a water-soluble acid or base is contained in the fuel oil composition A. If the test result is acidic or alkaline, it means that the fuel oil composition A contains a water-soluble acid or base. If the test result is neutral, it means that the fuel oil composition A does not contain a water-soluble acid or base. As mentioned above, the reaction is measured by the method specified in JIS K 2252 (1998) "Petroleum products - Reaction test method." Specifically, water is added to the sample, and the sample is heated and shaken to extract the acid and base into the aqueous phase. Methyl orange or phenolphthalein is used as an indicator to determine whether the extracted aqueous phase is acidic, neutral, or alkaline, thereby determining the presence or absence of the acid and base in the sample. In the fuel oil composition A of the present invention, the reaction is neutral, which enables the fuel oil composition A to exhibit excellent storage stability in fuel tanks and fuel piping.
[0059] The fuel oil composition A according to the present invention preferably has a flash point of 60.0°C or higher, more preferably 70.0°C or higher, and even more preferably 80.0°C or higher. The heavy oil composition A according to the present invention has a flash point of 60.0°C or higher, which makes it easier to handle.
[0060] The pour point of the A fuel oil composition according to the present invention is preferably -10.0°C or lower, more preferably -15.0°C or lower, and even more preferably -20.0°C or lower. By ensuring that the pour point of the fuel oil composition A according to the present invention is −10.0° C. or lower, the fluidity of the fuel oil composition A can be suitably ensured even in cold regions in winter. There is no particular lower limit for the pour point of the fuel oil composition A according to the present invention, but the pour point of the fuel oil composition A according to the present invention is usually -60.0°C or higher.
[0061] The cetane index of the A fuel oil composition according to the present invention is preferably 40.0 or higher, more preferably 50.0 or higher, and even more preferably 55.0 or higher. When the fuel oil composition A according to the present invention has a cetane index of 40.0 or more, a good combustion state can be obtained when the fuel oil composition A is combusted.
[0062] The fuel oil composition A of the present invention can be prepared by mixing predetermined amounts of the above-mentioned isoparaffinic base material and animal and vegetable oils as essential base materials, and further mixing in known base materials or additives within ranges that do not impair the effects of the present invention.
[0063] When the above-mentioned isoparaffinic base material and animal and vegetable oils are mixed to prepare the A fuel oil composition according to the present invention, the order of mixing is not particularly limited.
[0064] The A fuel oil composition according to the present invention may contain various additives in addition to the above base constituents. The additives include one or more selected from known fuel additives such as anti-icing agents, antioxidants, metal deactivators, anti-static agents, lubricity improvers, conductivity adjusters, and corrosion inhibitors.
[0065] According to the present invention, it is possible to provide a heavy oil composition A that can be composed exclusively of a fuel oil base material made from renewable raw materials and that can exhibit excellent low-temperature fluidity without the addition of a cold flow improver (CFI). [Example]
[0066] The present invention will be described in more detail below based on examples and comparative examples, but the present invention is not limited to these examples in any way.
[0067] (base material) The following substrates were used in the following examples and comparative examples. The properties of each substrate are shown in Table 1. Isoparaffinic base oil 1 (IP base oil 1) Contains 100.0% isoparaffins by volume (100.0% isoparaffin content by volume, 0.0% n-paraffin content by volume, and 0.0% aromatics content by volume). Isoparaffinic base oil 2 (IP base oil 2) Contains 100.0% isoparaffins by volume (100.0% isoparaffin content by volume, 0.0% n-paraffin content by volume, and 0.0% aromatics content by volume). Hydrodesulfurized kerosene (straight run kerosene) It is a kerosene fraction (straight-run kerosene) obtained by atmospheric distillation of Middle Eastern crude oil and then hydrodesulfurized. Hydrodesulfurized diesel (straight-run diesel) It is a diesel fraction (straight-run diesel) obtained by atmospheric distillation of Middle Eastern crude oil and then hydrodesulfurized. Catalytic cracking diesel Cracked diesel distillate obtained from a fluid catalytic cracking unit. Petroleum residue fractions This is a product in which the viscosity of the vacuum distillation residual oil distilled from a vacuum distillation unit is adjusted with a light oil fraction, etc. In the following tables, the distillation properties (distillation temperature) of the isoparaffinic base material were measured by the gas chromatograph distillation test method specified in ASTM D6352, and the distillation properties (distillation temperature) of straight-run kerosene, straight-run diesel oil, and catalytically cracked diesel oil were measured by the method specified in the "atmospheric pressure distillation test method" specified in JIS K 2254:1998 "Petroleum products - Distillation test method."
[0068] In the tables below, a sulfur content of "<1" means less than 1 ppm by mass, a residual carbon content of "<0.01" in 10% residual oil means less than 0.01% by mass, an ash content of "0.001" means less than 0.001% by mass, and a moisture content of "<100" means less than 100 ppm by mass.
[0069] [Table 1]
[0070] (Examples 1 to 13, Comparative Examples 1 to 5) In addition to the above base materials (IP base oil 1, IP base oil 2, straight-run kerosene, straight-run diesel, catalytic cracking diesel, petroleum residual fraction), safflower oil, sunflower oil, rice oil, olive oil, and rapeseed oil were prepared as edible oils, and each of the heavy oil compositions A according to Examples 1 to 13 and Comparative Examples 1 to 5 was prepared by blending these in the proportions shown in Tables 2-1 and 2-2. The properties of each of the resulting fuel oil compositions A are shown in Tables 3-1 and 3-2. In the following table, the distillation properties (distillation temperature) of the A heavy oil composition containing an isoparaffinic base material were measured by the gas chromatograph distillation test method specified in ASTM D6352.
[0071] In the table below, a kinematic viscosity of "<10,000" at 50°C means a viscosity of 10,000 mm 2 / sec; a sulfur content of "<1" means less than 1 ppm by mass, respectively; carbon residue in 10% residual oil of ">0.29", ">0.27", and ">0.28" means more than 0.29 mass%, more than 0.27 mass%, and more than 0.28 mass%, respectively; an ash content of "<0.001" means less than 0.001 mass%, a water content of "<100" means less than 100 ppm by mass, and a pour point of "<-60.0" means less than -60.0°C.
[0072] [Table 2-1]
[0073] [Table 2-2]
[0074] [Table 3-1]
[0075] [Table 3-2]
[0076] From Table 1, Table 2-1 and Table 3-1, it can be seen that the A heavy oil compositions according to the present invention obtained in Examples 1 to 13 contain 65.0 to 96.5% by volume of a predetermined isoparaffinic base material and 3.5 to 35.0% by volume of animal and vegetable oils, have a residual carbon content of 0.20% by mass or more in 10% residual oil, and have a kinematic viscosity at 50°C of 10,000 mm 2 / seconds or less. Therefore, it can be seen that the heavy oil composition A obtained in these examples can be composed of biomass or a base material made from biomass, and can exhibit excellent low-temperature fluidity without the addition of a cold flow improver (CFI).
[0077] On the other hand, from Table 1, Table 2-2 and Table 3-2, it can be seen that the A heavy oil compositions obtained in Comparative Examples 1 to 5 did not contain the predetermined amounts of isoparaffinic base material and animal and vegetable fats and oils (Comparative Examples 1 to 4), and were composed of a conventional petroleum base material and carbon residue adjuster and did not contain a cold flow improver (CFI) (Comparative Example 5). Therefore, the carbon residue content in the 10% residual oil was less than 0.20 mass% (Comparative Examples 1 and 3), and therefore did not satisfy the requirements of the Tax Law for A heavy oil compositions, and the kinematic viscosity at 50°C was less than 10,000 mm 2 / sec (Comparative Example 2), the pour point was less than -60°C (Comparative Example 3), and a large amount of sludge was detected (Comparative Examples 4 and 5), indicating that the low-temperature fluidity was poor. [Industrial Applicability]
[0078] According to the present invention, it is possible to provide an A heavy oil composition that can be composed exclusively of biomass or a base material made from biomass as a raw material, and that can exhibit excellent low-temperature fluidity without the addition of a cold flow improver (CFI).
Claims
[Claim 1] The sulfur content is less than 10 ppm by mass, the isoparaffin content is 85.0% by volume or more, the n-paraffin content is 7.0% by mass or less, the aromatic content is 0.5% by volume or less, and the density at 15°C is 0.7900 to 0.8200 g / cm 3 , containing 65.0% to 96.5% by volume of an isoparaffinic base oil having a distillation range according to ASTM D 6352 of 160.0°C to 480.0°C; Contains 3.5 to 35.0% by volume of animal and vegetable oils and fats, Residual carbon content in 10% residual oil is 0.20% by mass or more, Kinematic viscosity at 50°C is 10.000 mm 2 / seconds or less A heavy oil composition A characterized by:
Citation Information
Patent Citations
Fuel oil composition
JP2003292977A
A-type heavy oil composition
JP2006052316A
Heavy oil a composition
JP2017149979A
Liquid fuel
US20210163836A1